final report - final report integration of suspended particulate matter and oil transportation study...
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FINAL REPORT
Integration of Suspended Particulate Matterand Oil Transportation Study
(Contract No. 14-12-0001-30146)
September 15, 1987
Submitted to:
Minerals Management ServiceEnvironmental Studies949 East 36th Street
Anchorage, Alaska 99508
Submitted by:
J.R. Payne, B.E. Kirstein, J.R. Clayton, Jr., C. Clary,R. Redding, D. McNabb, Jr., and G. Farmer
Science Applications International Corporation10260 Campus Point Drive
San Diego, CA 92121
TABLE OF CONTENTSSection
1.0 INTRODUCTION...................................................... 1-1
1.1 BACKGROUND AND RELEVANCE OF OIL/SUSPENDED-PARTICULATE-MATERIAL INTERACTIONS TO OCS OIL AND GAS DEVELOPMENT......... 1-2
1.2 MODELING APPROACH FOR OIL/SPM INTERACTIONS................... 1-121.2.11.2.21.2.3
Dispersion of Oil Droplets .Sediment Transport .Interaction of Crude Oil with SuspendedParticulate Material .
1-161-21
1-23
1.3 OIL/SPM INTERACTION MODEL DEVELOPMENT........................ 1-26
1.3.1 Formal Description of Suspended Particulate Matterand Oil Interactions.... 1-28
1.3.2 Detailed Discussion of Oi1-SPM Kinetics............... 1-32
2.0 EXPERIMENTAL MEASUREMENTS OF OIL-DROPLET AND SUSPENDED-PARTICULATE-MATTER KINETICS....................................... 2-1
2 .1 BACKGROUND................................................... 2-1
2.2 EXPERIMENTAL TECHNIQUES AND RESULTS.......................... 2-5
2.3 IMPLICATIONS FOR MODEL DEVELOPMENT........................... 2-30
2.3.12.3.2
Application of Oi1·SPM Kinetic Equations .Kinetic Algorithm Use in an Ocean Circula-tion Model .
2-30
2-34
2.4 RESULTS OF OIL/SPM INTERACTION KINETICS DETERMINATIONSUSING A 28 LITER STIRRED CHAMBER............................. 2-35
2.4.1 Background, Required Assumptions and Limitationsof Experiments..... ................................... 2-35
2.4.2 Results and Discussion of Experiments with FreshPrudhoe Bay Crude Oil, 2-Day Weathered Crude Oil,12-Day Weathered Crude Oil and Jako1of Bay SPM...... .. 2-44
'2.4.2.1 Oi1/SPM Interaction Rate Constant withFresh Prudhoe Bay Crude Oil.................. 2-44
2.4.2.2 Oi1/SPM Interaction Rate Constant with2- and 12-Day Weathered Crude Oil............ 2-51
i
TABLE OF CONTENTS (continued)Section
3.0 CHEMICAL PARTITIONING AND PHYSICAL BEHAVIOR OF DISPERSEDOIL DROPLETS AND OIL/SPM AGGLOMERATES.......... 3-13.1 SEPARATION AND ANALYSIS OF SPM AND DISPERSED OIL
FRACTIONS. ................................................... 3-1
3.1.1 Method Validation for Polyester Filter-VacuumFi1tration Procedure. ................................. 3-2
3.2 UTILIZATION OF THE OIL SEPARATION TECHNIQUE IN OIL-SPMINTERACTION AND SEDIMENTATION RATE STUDIES................... 3-8
3.2.1 Oi1-SPM Sedimentation Rate Studies.................... 3-11
3.2.1.1 FID-GCAna1yses of Oil Fractions in theSedimentation Experiment..................... 3-13
3.2.2 SPM Load and Hydrocarbon Information from Oi1-SPMInteraction Studies with the 28 Liter StirredChamber, System ,...................... .3-18
3.2.2.1 Effect of Prior Weathering History ofPrudhoe Bay Crude Oil on SPM Loads andDispersion of Oil into the Water ColumnOver Time ,...................... 3-19
3.2.2.2 Distribution of Oil Between Dispersed,Dissolved and SPM Phases in ExperimentsWith Fresh, 2-day and .12-day WeatheredOil.......................................... 3-22
3.2.2.3 FID-GC Analyses of Oil Fractions in theSPM and Dispersed Oil Phases of Experi-ments in the 28 Liter System.... ............. 3-22
3.3 PARTITIONING OF DISSOLVED PETROLEUM HYDROCARBONS BETWEENSEDIMENT AND WATER. .......................................... 3-28
4.0 MODELING OF PHYSICAL PROCESSES INVOLVED WITH THE INTERACTIONOF OIL DROPLETS AND SPM IN THE WATER COLUMN....................... 4-1
4.1 WATER COLUMN PROCESSES....................................... 4-1
4.2 BOUNDARY CONDITIONS. ......................................... 4-4
4.3 WATER COLUMN PROCESSES....................................... 4-6
4.4 COMPONENT MODELS OF OIL-SPM TRANSPORT AND FATE... ............ 4-8
ii
\,
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TABLE OF CONTENTS (continued)
Section Page
5.0 APPLICATION OF THE GRANT-MAnSEN-GLENN BOUNDARY LAYER MODELTO A MODEL OF SUSPENDED PARTICULATE TRANSPORT.. 5-1
5.1 INTRODUCTION '........................................ 5-1
5 .2 MODEL ELEMENTS. .............................................. 5-2
5.2.15.2.25.2.35.2.45.2.55.2.65.2.7
Boundary Layer Hydrodynamics .Initiation of Sediment Motion .Sediment Suspension .Reference Sediment Concentration .Suspended Sediment Stratification Effects .Bedload and Suspended Sediment Transport .Bottom Roughness ',' .
5-25-65-8
5-115-125-135-15
5.3 RUNNING THE GMG MODEL........................................ 5-18
5.4 APPLICATION TO A SUSPENDED PARTICULATE FLUX MODEL............ 5-24
5.4.15.4.2
Interfa~ing with a Wave Prediction Model .Problems .
5-285-28
5.5 APPENDIX: FRICTION FACTOR, SHEAR STRESS AND SHEARVELOCITY SOLUTIONS. .......................................... 5-29
6 .0 EXECUTIVE SUMMARy................................................. 6-1
7.0 BIBLIOGRAPHY...................................................... 7-1
APPENDIX A COMPOUND SPECIFIC HYDROCARBON CONCENTRATIONS FROM 28 LITERSTIRRED CHAMBER EXPERIMENTS................................ A-1
APPENDIX B TABLE OF MATHEMATICAL EXPRESSIONS. ......................... B-1
iii
Table
1-1
1-2A
1-2B
1-3
2-1
2-2
2-3
2-4
2-5
2-6
2-7
2-8
2-9
2-10
2-11
3-1
LIST OF TABLES
Results of equilibrium partitioning oi1/SPM interactionstudies .
Total organic carbon (TOC) and microscopic composition ofsediments .
Sediment mineralogy as determined by x-ray diffraction .
Observed Energy Dissipation Rates .
Thursday - November 6, 1986, 11:30 a.m. OIL-SPM,Half Field , .
Thursday - November 6, 1986, 3:00 p.m. OIL-SPM,Half Field .
Thursday - November 7, 1986, 5:00 p.m. OIL-SPM,Full Field .
Thursday - November 8, 1986, 10:45 a.m. OIL-SPM,Half Field/Full" Field .
Thursday - November 6, 1986, 10:50 a.m. OIL ONLY,Full Field .
Friday - November 7, 1986, 8:00 a.m. OIL ONLY,Full Field .
Saturday - November 8, 1986, 3:20 a.m. OIL ONLY,Full Field .
Oil/SPM Interaction and Sedimentation Experiments .
Oil/SPM Interaction and Sedimentation Experiments .
Chemical and Physical Characteristics of Oil from WaveTank #4 Oil/SPM Interaction Experiment .
Values for m and k (equations 2-37 through 2-39) calcu-lated from data plots in Figures 2-16 and 2-17 .
Polyester Filter vs. NOAA Status and Trends SedimentExtraction Comparison .
iv
1-5
1-6
1-7
1-18
2-11
2-12
2-13
2-14
2-15
2-16
2-17
2-18
2-19
2-41
2-48
3-7
3-2
5-1
5-2
LIST OF TABLES (continued)
Partitioning Experiment Results .
Some results for neutral, near-bottom model run for amoderate storm wave on the continental shelf, as describedin text '" .
Some results for stratified near-bottom model run for amoderate storm wave, strong current, and a silt bed onthe continental shelf .
v
3-30
5-22
5-25
Figure
1-1
1-2
1-3
1-4
2-1
2-2
2-3
2-4
2-5
2-6
2-7
2-8
2-9
2-10
LIST OF FIGURES
Flame ionization detector capillary gas chromatogramsfrom KB-4 (Seldovia River Salt Marsh) oil/SPM interactionstudies .
Illustration of differential volume element used to derivemomentum transport equation(s), or continuity equation .
Illustrations of possible oil/SPM interactions showingtransport and reaction paths .
"Collision" Sphere of Radius a, which denotes the collisiongeometry for monodispersed spheres of diameter a .
Experimental Hardware Used to Determine Oil-SPM InteractionKinetics .
Execution of 4-liter oil/SPM interaction experiment at theNOAA Kasitsna Bay field laboratory .
Microscope Slide Arrangement for Viewing Oil Dropletsand SPM .
Oil/SPM Interactions Free Oil Count .
Oil Interactions (Oil Only) .
Oi1-SPM Interactions Total Free SPM .
Experimental Hardware to Measure the Power Dissipated ina Stirred Vessel .
Determination of weight required to achieve 400 rpmstirring turbulence in the 4-1iter beaker experiments .
Construction of the binary counting circuit board usedto accurately measure rpm in the 4-1iter beaker oil/SPMinteraction experiments : .
Trigger mechanism attached to the stirrer shaft andbinary counting circuit board (in the background adjacentto the battery power supply) for the experimental rpmdeterminations .
vi
1-8
1-14
1-24
1-33
2-6
2-7
2-9
2-20
2-21
2-22
2-25
2-26
2-27
2-28
Figure
2-11
2-12
2-13
2-14
2-15
2-16
2-17
2-18
3-la
3-lb
3-lc
3-ld
3-2
LIST OF FIGURES (continued)
Prototype tank design for evaporation/dissolution andoil/SPM interaction experiments.......... 2-37
Twenty-eight liter oil/SPM interaction chamber equippedwith directional air manifold and stirring motor forintroduction of turbulence.................................... 2-38
Dispersed oil droplets and SPM in the 28 liter stirredreaction chamber using l2-day weathered Prudhoe Baycrude oil and <54 ~m sieved Jakolof Bay SPM 2-39
Twenty-eight liter oil-SPM interaction chamber containingresidual dispersed oil droplets and SPM two minutes aftertermination of stirring turbulence............................ 2-40
Idealized time-series profiles of free oil (C ), freeSPM (C ) and oiled SPM loads in 28 liter stir~ed chamberexperi~ents. .................................................. 2-45
Dispersed oil concentrations (mg total resolved hydro-carbons/liter of seawater) over time (hours after thespill event) for experiments with fresh, 2-dayweathered and l2-day weathered Prudhoe Bay crude oil.......... 2-46
Natural logarithms of the ratios of SPM concentrations attime = "t" hours to that at time = 0 hours versus time inexperiments with fresh, 2-day weathered and l2-day weath-ered Prudhoe Bay crude oil and no oil addition................ 2-47
Computer generated plots of product concentrations (~g oilS PM/liter seawater) versus time (hours after spill event)for values of Q ranging from 0.03 to 0.12..................... 2-50
Unweathered Prudhoe Bay crude oil used for experimental oil-SPM-water system.............................................. 3-4
"Dissolved phase" from experimental oil-SPM-water system...... 3-4
"SPM phase" from experimental oil-SPM-water system............ 3-5
Second methylene chloride rinse of filter from "SPM phase"in Figure 3-lc ................................................ 3-5
Gravimetric concentrations of SPM in sedimentation experi-ments conducted with oiled and unoiled Jakolof Bay sediments(sieved to <53 ~m)............................................ 3-12
vii
~-------------------------------------------"
LIST OF FIGURES (continued)
Figure
3-3(a) Concentration rati?s of n-~lka~es to nC21 in.oil samplesfrom the parent o~l-SPM k~net~cs rate exper~ment.............. 3-14
3-3(b) Comparable concentration ratio information for selectedaromatic compounds............................................ 3-14
3-4(a) Absolute concentrations of n-alkanes associated with"sedimented" and "residual suspended" SPM fractions after110 minutes of settling in the oiled sedimentationexperiment '............................................. 3-16
3-4(b) Comparable concentrations for aromatic hydrocarbons.......... 3-16
3-5(a) Concentration ratios of n-alkanes to nC2l in the initialblended oil (2 minutes after blending) and the final"sedimented" and "residual suspended" SPM after 110 min-utes of settling in the oiled sedimentation experiment. ...... 3-17
3-5(b) Comparable concentration ratio information for selectedaromatic compou~ds (see Figure 3-4(b) for compoundidentification) .............................................. 3-17
3-6(a) SPM loads over time in experiments with fresh, 2-dayweathered and l2-day weathered Prudhoe Bay crude oil andwith no oil addition in the 28 liter stirred chambersystem..................................................... ... 3-20
viii
3-6(b) Dispersed oil concentrations in the correspondingexperiments with oiL........................................ 3-20
3-7(a) Concentrations of oil (i.e., total resolved hydrocarbons)over time in the dispersed oil, dissolved and SPM phases ofwhole water samples from the experiment with fresh PrudhoeBay crude oil in the 28 liter stirred chamber system......... 3-23
3-7(b) Comparable information from the experiment with 2-dayweathered Prudhoe Bay crude oil.............................. 3-23
3-7(c) Comparable information from the experiment with 12-dayweathered Prudhoe Bay crude oil (cont.)...................... 3-24
3-8(a) Absolute concentrations of n-alkanes associated with"sedimented" and "residual suspended" SPM fractions atthe final sampling time in the 28 liter stirred chamberexperiment with 2-day weathered Prudhoe Bay crude oil........ 3-26
Figure
3-8(b)
3-9(a)
3-9(b)
4-1
4-2
4-3
5-1
5-2
5-3
6-1
6-2
6-3
LIST OF FIGURES (continued)
Comparable concentrations for selected aromatic compounds(napth - naphthalene; see Figure 3-4(b) for other compoundidentification .
Concentra~ion r~tio.information for n-alkanes to nC2l fromthe exper1ment 1n F1gure 3-8 .
Comparable information for aromatic compound ratios inFigure 3-8 .
Sketch of water column processes affecting the distribu-tion of oil and SPM .
Sketch of a plan view of oil-SPM transport processes .
Component Models of a 3-D oil-SPM transport model .
Extended Shields Curve .
Flow chart tracing computational procedure for boundarylayer model. Labels are referred to in text .
Predicted neutral and stratified velocity and concentra-tion profiles to a height z = 0 /6 for a moderate storm wavewith a moderate storm wave withCa reference current of26 cmy's ec .
Plots of In (oil droplet number density) vs time forexperiments with fresh Prudhoe Bay crude oil and GrewingkGlacier till. The energY3dissipation rate constant (f) wasapproximately 260 ergs/cm sec in each experiment. (a) oilplus glacial till. (b) oil only .
Photomicrograph of blended oil droplets on microscopeslide .
Photomicrograph of oil-SPM agglomerates on microscopeslide .
ix
3-26
3-27
3-27
4-3
4-10
4-11
5-9
5-19
5-23
6-6
6-7
6-8
ACKNOWLEDGEMENTS
Various consultants have contributed greatly to this project over aperiod of many months. The late Dr. William Grant of Woods Hole OceanogrpahicInstitution provided initial guidance and review on modeling bottom boundarylayer conditions as influenced by wind and wave turbulence. With Dr. Grant/suntimely passing, W.R. Geyer provided additional assistancce with his review ofbottom boundary layer modeling, and he was in essence responsible for the prep-aration of Section 5 of this report in its present form. Mr. Wilson Hom andDr. Tom Fogg are acknowledged for their assistance and contributions in themathematical derivations of the reaction rate constants measured in the 28 li-ter stirred chamber system. Gas chromatography/mass spectrometry analyses werecompleted by Mr. Gary Smith. The photographic prints presented in this reportwere prepared by Larry Haynes of Design Photogaphics. Lucy Kaelin, MabelO/Byrne and Laurie Hughey are thanked for their tireless efforts on the wordprocessor and for their assistance in the preparation of this report in itspresent form.
1.0 INTRODUCTION
The objective of this study was to characterize the nature ofoil/suspended particulate material (SPM) interactions such that mathematicalformu1ation~ could be derived and (ultimately) incorporated into an oceanoil-spill trajectory and circulation model. This report details the resultsand findings from experiments and derivations which have been completed to dateand contains suggestions for areas of additional study.
The remainder of Section 1 contains a review of previous oi1/SPMinteraction studies, the derivations and assumptions necessary to model theseinteractions (including uncertainties on oil droplet dispersion, turbulence re-quirements, and oi1/SPM kinetics). Section 2 presents the derivations andresults from laboratory studies completed to measure the reaction rate constantfor oi1/SPM binding, and interestingly, similar results were obtained with twovery different experimental systems. Section 3 contains the results of chemi-cal characterizations of the selective partitioning behavior which occurs amongthe discrete phases of dispersed oil droplets, dissolved oil constituents, free(un-oiled) SPM, oi1ed-SPM agglomerates still in suspension and sedimentedoi1-SPM which has been removed from the water column. Section 4 presents anoverview of the potential computer requirements (and limitations) for modelingoi1/SPM interactions within the context of a full three-demensiona1 ocean cir-culation model. Section 5 presents an overview of the late Dr. William Grant'scontribution to modeling the bottom boundary layer and sediment resuspension/transport as controlled by wave and current regimes. Section 6 contains anexecutive summary of major program elements, problems encountered inexperimental and modeling efforts, and solutions derived and used to achievethe re~u1ts presented. Finally, Section 7 is the bibliography of all citedliterature, and the Appendix contains all of the reduced compound specificoi1/SPM concentration data obtained from FID-GC and GC/MS analyses of samplescollected. These data can ultimately be combined into boiling point ranges toallow comparison of oi1ed-SPM composition with Open-Ocean Oil Weathering Modelpredictions of oil composition by distillate cuts.
1-1
It is not insignificant that several important program elements (e.g.,wave and current induced sediment resuspension and transport, breaking wave-induced oil droplet dispersion and turbulent energy dissipation rate predic-tions) are all areas of on-going Ph.D.-level research in universities, oceano-graphic institutions and private laboratories. As a result, there are stillmany gaps in our knowledge. At this time it would be premature to believe thata fully operational three- demensiona1 ocean circulation model that incorpor-ates all of the desired interaction terms (oil droplet dispersion, sedimentresuspension for all size classes of SPM, oi1/SPM collisions as a function ofoil and SPM loadings and turbulence, etc.) is possible in the very near future.As discussed in Section 4, there are several possible approaches includingfinite element circulation models based on conservation of mass and energy aswell as probability distribution functions (PDFs) which might be used toapproximate the problem. In any case, extensive computer capabilities andresources may be required to ultimately develop predictive models that incor-porate all of the variables and stochastic processes involved.
1.1 BACKGROUND AND RELEVANCE OF OIL/SUSPENDED-PARTICULATE-MATERIAL INTER-ACTIONS TO OCS OIL AND GAS DEVELOPMENT
The fate of hydrocarbon contaminants released into the outer continen-tal shelf waters of Alaska will be controlled by simultaneous physical (e.g.circulation, sediment transport and deposition), chemical (oil weathering andoil/suspended particulate material interactions), and biological (microbial)processes (Payne et a1., 1984; Atlas et al., 1983). Interactions between spil-led oil and suspended particulate material (SPM) represent a major potentialpathway for the dispersal and deposition of petroleum hydrocarbons in coastalenvironments, particularly in areas characterized by naturally high concentra-tions of river-derived and bottom-resuspended SPM.
The ability to predict the water column residence times and eventualsinks for hypothetical oil spills facilitates predictions of effects to poten-tially impacted benthic ecosystems. Such predictions require a method for syn-thesizing and integrating representative data for dispersed oil and suspended
1-2
-.-
sediment concentrations, transport, deposition, and resuspension rates, as wellas sediment/oil partition coefficients under a variety of possible spill sce-narios.
Oil and SPM interactions occur through two primary mechanisms: (1) oildroplets colliding with suspended particulate material and (2) molecularsorption of dissolved species. The parameters and/or conditions that mightinfluence the rate of "reaction" between dispersed oil droplets and SPM arenumerous; the concentrations of dispersed oil and SPM, size distribution of theoil droplets and SPM, composition of the oil and SPM, and the density of theoil and SPM will all have some effect on the rate of oil droplet/SPMassociations and ultimate sedimentation. The solubility of individualhydrocarbon components in seawater also influences rates of molecular sorptionof dissolved species onto SPM (Quinn, in press; Boehm 1987). However, datafrom field and laboratory studies suggest that sorption of truly dissolvedcomponents is not important to the overall mass balance of an oil spill (Payneet al., 1987). Such adsorption may be important, however, for biologicalconsiderations as described below.
Sorption of oil onto suspended particles depends on the solubility be-havior of hydrocarbons and the nature of the particles. In general, a greaterwater solubility of a particular hydrocarbon component accompanies a reducedtendency to associate with particulate matter (Gearing et al., 1980). Differ-ences in solubility and adsorption behavior subsequently may result in a frac-tionation of the oil, with soluble lower molecular weight aromatic hydrocarbonsenriched in the water phase, and relatively insoluble higher molecular weightcomponents associated with the suspended particulate phase. However, changesin salinity, pH, turbulence, temperature, concentrations of oil, and presenceof natural surfactants (dissolved organic matter) will also influence the par-titioning of oil onto SPM (Quinn, in press). The affinity of a particular hy~drocarbon component for particulate adsorption is described by the partitioncoefficient (or adsorption efficiencies) (K ) such that K = e /e , where e is
p p P w Pthe concentration of the hydrocarbon on a given weight of particles and e iswthe concentration of the hydrocarbon in an equal weight of water.
1-3
As part of an Open Ocean Oil Weathering Program, SAIC measuredcompound-specific partition coefficients between fresh Prudhoe Bay crude oiland four representative sediment types characteristic of suspended particulatematerial encountered in Alaskan Outer Continental Shelf waters (Payne et al.1984). Table 1-1 presents the SPM/water phase concentrations obtained on spe-cific aromatic compounds from those measurements. Tables l-2A and l-2B presentinformation regarding the chemical and visual (i.e., microscopic) compositionof the sediment types. Figure 1-1 presents representative chromatograms show-ing the preferential partitioning of lower molecular weight aromatics (i.e.,shorter retention times in Figure l-lG) into the water column and intermediateand higher molecular weight aromatic and aliphatic hydrocarbons (i.e., longerretention times in Figures l-lA and D) partitioning onto the suspendedparticulate material.
Gearing et al. (1979) also reported the fractionation or partitioningof lower molecular weight aromatic compounds (including up to 3-ring aromatics)into the dissolved phase before adsorption of the oil onto suspended particu-late material and subsequent sinking. In test tank studies completed at theMarine Ecosystem Research Laboratory at the University of Rhode Island, thearomatic/aliphatic ratio in the sediment was much lower than that in the parentoil suggesting that preferential dissolution of lower molecular weight aromaticcompounds may be occurring. Specifically, 2-35% of the higher molecular weightaliphatic, acyclic and greater than 3-ring hydrocarbons were adsorbed onto thesuspended particulates and sediments in contrast to 0.1% of the more watersoluble naphthalene and methylnaphthalene components which were the predominantaromatic materials in the No.2 fuel oils used in their studies.
Winters (1978) observed similar partitioning in two simulated oilspills and one mixture of aromatic compounds added to a test tank. Thepetroleum-derived alkanes were approximately 10 times greater in the particu-late fraction, and the lower molecular weight aromatics were at least 5 timesmore concentrated in the dissolved phase.
In samples of suspended particulate material collected along transectsperpendicular to the South Texas OCS near Corpus Christi, Parker and Macko
1-4
Table 1-1. Results of equilibrium partitioning oil/SPM interaction studies(From Payne et al .• 1984)AIII'IIAIIC fRACTION••
AROflATIC fRACTlOll."Benzenes
NaphthalenesPhenanlhrelles
luta l Inta l /:n-alk Total Total '.4&1.J-dlQ!lhy' elh)'1 naphthalene 2-__ 'h)'11-lI1ethil 2-elh)'1 2.J-dilllelh)'1 1.6,1- trl-eth)" phenanlhrene 7-olelhy'
«).III~JIf' • Res OCM /n-~I~ .~iiii~~~~..Ile~ ___ !!~_____I~~t 1~7~J ___ l!1~t (1305) _ OJ?? 114ll.4) _ II ~J.fl) .mw_ (1788) 119(4)~ 1I"y-'\,..rlinN·nl 340,011O n.eeo 26.000 0.08 46,000 42.000 15 62 40 630 400 10J 440 290 570 J90A',uP-I"" '·hll~(> 4.760 0 JJ 0.007 601 75 2.9 0.56 I.J 7-4 7.4 9.8 J.I 1.0 0.23K. lI"y-?A
18,000 16.000 0.02 385.000 1.100 270 90 . 550 JIO 240 143 8J
Sed i"",11 I 795,00046
96 200A""I'OIls Phase J,.l8O 0 II O.OOJ 1.907 0 J.4 1.4 J.J 7.2 6.8 0.7 2.2 1.0K. 1I"v ,'II\,',liull'u' Ml.llllO 51,000 14.000 0.02 9,600 22.0001\""1'1111', I"M\I' I/O 0 17 0.1 2,720 0~. Ody-JSpdlllll'ni 85.000 10,000 5.000 0.06 12.00'J 10.000 JJ IJO 4 91 8J 25 89 J5 44A'/lIe,." PhaSP 5,840 0 B 0.001 512 0 2.0 0.74 0.6J 4.4 0.28 2.J 0.28 0.53k. O,'y-4•... ~'"l111'lIt 253,000 262.000 60.000 O.J 44.000 15,000 12 200 29 48 J70 125 JJl 210 71
IVI IIlJ1,eollS"ltase Nol reduced 2.180 0 2.9 0.46 0.16 0.49 I.J 0.12 2.2 0.J4
ver), low
'k. lIay-I--Grew'ngh GlacIer TIllk. lIdy·211-Chlna Poot Bay surface I c.k. Bdy-lD-Chlna Poot Bay depth I-B c.k. 8dy -J- -kas It sna Bay consolidated sedl-entk. Oa,-4--Seldnvla River salt •• rsh
··Selll •••nl concentration In "9/k9, water concentration In pgll
·"Sedhllenl cflllceniration In 1'9/lg, water concentration In pg/I; nllllbers In parentheses are con~ound kovat indites.
TABLE 1-2A. Total Organic Carbon (TOC) and Microscopic Composition of Sediments
GENERAL COMPOSITION
almost entirely clay fragments
diatoms, terrestrial plant material,clay fragments
mostly clay fragments, some diatomsand terrestrial plant material
mostly diatoms, some clay fragments
mostly organic debris and fecalpellets, a few diatoms, very few·clay fragments
organic debris and clay fragments
1-6
TABLE 1-2B. Sediment Mineralogy as Determined by X-Ray Diffractiona
COMPOSITON (%)
SEDIMENT SOURCE-Quartz Kaolinite Feldspar Calcite Sodiun ChlorideMica Other
KB-1 (Grewingk Glacier till) >50 20-40 20-40 None <2 None
KB-3 (Kasitsna Bay) >50 5-10 20-40 None None 2-5 Gypsun <2
KB-4 (Seldovia salt marsh) >50 5-10 20-40 None None 2-5
KB-5 (Jakolof Bay) >50 10-20 20-40 <2 None 2-5
I-"I a....• ~ Analyses completed by Technology of Minerals - 2030 Alameda Padre Serra, Santa Barbara, CA 93103
)o2••,
f 7A
•
B
c
o
,.... ,f a
N.j
E
G
Figure 1-1. Flame ionization detector capillary gas chromatogramsfrom KB-4 (Seldovia River Salt Marsh) oil/SPM interactionstudies: (A) Aliphatic hydrocarbons in the oil exposedsediments; (B) Background level aliphatic hydrocarbonsmeasured in unexposed sediment; (C) Aliphatic hydrocar-bons in the water column extract; (D) Aromatic hydrocar-bons in the oil exposed sediments; (E) Background levelaromatic hydrocarbon components measured in the unexposedsample; and (G) Aromatic.hydrocarbons in the water columnextract. (From Payne et al.. 1984)
1-8
(1978) noted that the concentrations of higher molecular weight (nC-28 throughnC-30) compounds remained relatively constant with distance from the shore,whereas the total particulate hydrocarbon burdens decreased with increasingdistance. These authors attributed this to the introduction and sorption ofthe hydrocarbons near the shore with subsequent movement of particulate-boundoil and preferential retention of the higher molecular weight compounds duringweathering. Several higher molecular weight polynuclear aromatic hydrocarbonswere also identified on the particulate material, including alkyl-substitutednaphthalenes, phenanthrenes, dibenzothiophenes, fluoranthene and pyrene. Con-centrations of these materials were too low for quantitation; however, theycould be detected by selected ion monitoring GC/MS.
Selective partitioning of lower and higher molecular weight compoundshas also been observed by deLappe et al. (1979) in a study designed to measurethe partitioning of petroleum hydrocarbons among seawater, particulates, andthe filter feeding mussel, Mytilus californianus. Payne et al. (1980) andBoehm and Fiest (1980) also observed a similar partitioning between lower andhigher molecular weight compounds in the dissolved phase and suspendedparticulate material samples removed by filtration of large volume watersamples obtained in the vicinity of the IXTOC-l blowout in the Gulf of Mexico.
In a laboratory study, Meyers and Quinn (1973) found that the hydro-carbon adsorption efficiency (for the less than 44 ~m particle sized fractions)decreased in the order of bentonite> kaolinite> illite> montmorillonite.When Meyers and Quinn treated sediment samples from Narragansett Bay with 30%peroxide to remove indigenous organic material, an increase in adsorption po-tential was noted. The organic material (which was presumably humic sub-stances) was believed to mask the sorption sites on the sediment, thereby re-ducing the available surface area for adsorption of the organic compounds.Seuss (1968), on the other hand, suggested that a 3 to 4% organic materialcoating on clay will enhance sorption processes by providing, in effect, alipophillic layer to enhance non-polar hydrophobic binding. These findingswould be more in line with the results of Payne et al. (1984) in comparing the
1-9
adsorption potential of the organic-rich materials from the Seldovia Riverestuary to the composite diatom rich sediment samples from Kasitsna Bay (Table1-1).
In a laboratory study, Zurcher and Thuer (1978) considered the disso-lution, suspension, agglomeration and adsorption of fuel oil onto pure kaoli-nite. In their studies, the dissolved water column samples showed significantlevels of lower molecular aromatics in the benzene to methylnaphthalene range,and the adsorbed fraction contained n-alkanes and aromatics from Kovat indices1400 through 3200 (Kovats, 1958). The clay minerals in this experiment adsorb-ed about 200 mg of hydrocarbons per kilogram of dry material. Meyers and Quinn(1973) reported a similar value of 162 mg/kilogram for dry kaolinite. Payne etal; (1984) reported values from a low of 122 mg/kilogram (total resolved andUCM from both the aliphatic and aromatic fractions) from the SPM samples fromKasitsna Bay to a high of 1.2 g/kilogram for the 0 to l-cm subsamples from th~tidal mud flats from China Poot Bay.
While the results of these more recent oil/SPM interaction studiesusing representative samples from lower Cook Inlet parallel the findings re-ported by previous investigators, they are somewhat contradictory to resultsreported by Malinky and Shaw (1979). These authors examined the association oftwo lower molecular weight petroleum components and suspended sediments (pri-marily glacially-derived sediments from the south central Alaska region) andconcluded that sedimentation of oil by the adsorption to suspended mineral par-ticles may not be a major pathway for the dispersion of petroleum in the marineenvironment. In that study, however, they used l4C-labelled decane and bi-phenyl at near saturation levels (i.e., the ppm range, although exact concen-trations were not specified by the authors). In their experiments, the con-centrations of the two hydrocarbons associated with the sediments was approx-imately 30% of the original aqueous concentration in parts per million. Fromloadings of permitted discharges in Port Valdez and measured sediment loads,the authors calculated that less than 3% of the oil released into the harborcould be associated with the sediment. Thus, the authors concluded thatadsorption of hydrocarbons to suspended particulate material was not thatsignificant, and that the role of suspended mineral particulate material may be
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far less significant in adsorption of polynuclear aromatic hydrocarbons innatural waters than is the role of total suspended matter. The applicabilityof their findings to real oil spill situations in natural environments may belimited, however, in light of the fact that they did not use a natural oil oreven a water accommodated fraction of a natural oil, and by the fact that thecompounds which were utilized have significantly higher water solubilities thanthe higher molecular weight polynuclear aromatic hydrocarbons of interest.Clearly, the results of Payne et al. (1984) on glacially-derived till from theGrewingk Glacier (Table 1-1) show that the particulate material does have ahigh affinity for polynuclear aromatic hydrocarbons (inspite of its low TOC;see Table l-2A) and that the high surface area of the glacial till can providean active site for oil adsorption and ultimate sedimentation.
From the aforementioned equilibrium studies, it is clear that inter-actions between spilled oil and suspended particulates represent an importantmechanism for the dispersal and removal of oil from surface waters. Rates foroil/SPM interactions and dispersal are, in turn, related to concentrations ofsuspended materials and fluxes of SPM into and out of an impacted area. Inparticular, oil spills in nearshore waters with high suspended particulateloads experience rapid dispersal and removal of the oil due to sorption ontoSPM along frontal zones (e.g., Forrester, 1971; Kolpack, 1971). Boehm (1987)characterized the SPM concentration dependence on oi1/SPM fluxes as follows: atSPM concentrations from 1-10 mg/1iter, no appreciable transport of particle-associated oil to the benthos occurs; at SPM loads from 10-100 mg/liter, con-siderable oil/SPM interaction, with subsequent transport and deposition ispossible in the presence of sufficient turbulent mixing; and at SPM concentra-tions > 100 mg/liter massive oil transport may occur with potentials forsignificant adverse impacts to the benthos.
Consideration of dispersed oil droplets and SPM interactions are par-ticularly germane to predicting oil spill behavior in areas of high SPM loadssuch as Norton Sound where high SPM levels in nearshore waters are affected bythe Yukon River discharge. In this case, adsorption of dispersed oil onto sus-pended particulates may provide a relatively efficient mechanism for sediment-ing significant fractions of the oil mass. For example, following the TSESIS
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oil spill in the Baltic Sea, approximately 10-15% of the 300 tons of spilledoil were removed by sedimentation of SPM-adsorbed oil. The high oil flux wasdue to the large SPM concentrations resulting from turbulent resuspension ofbottom sediments (Johansson et al., 1980).
1.2 MODELING APPROACH FOR OIL/SPM INTERACTIONS
In this program we have utilized previously existing information (tothe greatest extent possible) and generated new data to develop a mathematicalmodel to quantify the interaction of oil with suspended particulate matter.The interaction kinetics of oil droplets and suspended particulate matter canbe used in a variety of "models." The original intent for the use of thekinetics was in conjunction with an existing ocean-circulation model whichcould add on a material balance calculation. However, since such anocean-circulation model is not easily accessible, work is now in progress thatwill illustrate how the kinetics (model) can be used. The models that arebeing considered are one-dimensional and will be accessible to otherresearchers by way of a personal computer. These models are intented toprovide "bounded" calculations and illustrate other concepts that must also beaddressed by an ocean-circulation model implementing the oil-spm kinetics.
It is important to note that the oil-spm interaction model that isbeing developed is intended to be an "add on" calculation for a generalcirculation model that addresses both vertical and horizontal transport. Sincea general circulation model must be used, it is necessary to describe how asuspended-particulate matter and oil-interaction description will "fit" into acirculation model. Circulation models are always finite-element numericalintegration codes, and as such, they require considerable effort in developmentand use. It must also be recognized that the description of the transport oftrace constituents in circulation models is usually an "add-on" calculation.For example, the transport of dissolved oil or small oil droplets in the watercolumn is an "add-on" because these constituents do not affect the momentumtransport calculations (i.e., circulation) in any measurable way.
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All circulation models are essentially solutions to momentum transportequations. For modeling purposes, sediment transport depends on ocean circula-tion. Consequently horizontal (x and y) and vertical (z) transport and timedimensions must be considered. Also included with the momentum transport equa-tion is the continuity equation in 3 dimensions. When these equations are ap-plied to specific boundary conditions, such as bottom topography, shoreline,and weather, a specific 3-D circulation model is obtained:' These models are"huge" because the large number of equations and the form of the boundary con-ditions make it impossible to "simplify" the mathematics. In essence, everydifferential element of the model affects every other differential element.
Weather is an important "driver" of circulation in these types ofmodels. In particular, wind energy transports momentum to the water column.This transferred momentum manifests "itself" in water velocity profiles whichin turn transfer momentum from the water column to the bottom, thus affectingsediment resuspension and deposition. These factors are considered in greaterdetail in Sections 4 and 5.
Figure 1-2 illustrates a differential volume element used to derivethe momentum transport equation(s). The arrows indicate inputs and outputs(momentum flux) to the volume. Arrows for inputs and outputs of sediment, oildroplets (as dispersed oil), and dissolved oil are also to be added to thisfigure.
Interactions of oil and sediment are described (mathematically) as oc-curring inside the volume element illustrated in Figure 1-2. Thus, for thesorption of dissolved oil onto sediment, partition ,coefficients (also calledsorptio~ efficiencies) relating dissolved oil and sorbed oil (on the solidsurface) are required. Taking the limit as ax, ~Y, ~Z, --> 0 yields thegeneral momentum balance equations along with the appropriate equations ofcontinuity (conservation of mass for water, oil species, and sediment).
1-13
•
•
Figure 1-2. Illustration of differential volume element used to derive
IIII "II
_______~I,'....
" ,
momentum transport equation(s), or continuity equation (r is
dJZmomentum flux, usually rxz - ~ dx
1-14
Two things of importance occur at the air-sea interface: (1) momentumis transferred to the water column from the "weather", and (2) oil is "in-jected" into the water column. The weather input at this boundary should begenerated by a stochastic weather model. Thus, when a request for oil trajec-tories is made, it is not correct to run just one trajectory because of thestochastic (probablistic) nature of the weather. It is necessary to run manytrajectory cases and then examine all of the trajectories to see the range ofcoverage and probable land hits. By including weather, and this weather mustbe an image of the past.meterological records, the specific site is truly con-sidered. Oil is also put into the differential volume element at the air-seaboundary.
When the differential volume element is on the ocean bottom or shore-line, boundaries exist where sediment is input into and taken out of the watercolumn, along with oil either as oil droplets, oil SPM-particle agglomerates,or dissolved oil. The sediment in the water column is described as a concen-tration. Since weather generates the shear stresses necessary for suspension(or deposition), a site-specific weather model must again be used.
Integrating an existing circulation model with the inputs of oil atthe air-sea interface and sediment from the bottom and shoreline will yield adescription of oil and SPM transport, and the interaction of these two addi-tional "species". These species will not affect the general circulation in anyway because their presence does not significantly affect momentum transport.Thus, the fate of oil and SPM depends on circulation (and weather) but circula-tion does not depend on oil and SPM. The defining equations for oil and SPMare t~us decoupled and essentially "ride along" as the momentum equations aresolved ..
The output, or predictions of such a model integration will be a sedi-ment material balance yielding water column concentrations of "oil" and SPM,and bottom concentrations of sediment (size and quantity) and oil in the sedi-ment. Therefore, the initial (time = 0) condition for sediment on the bottom
1-15
and in the water column must also be specified. This requires that asediment-inventory map of the entire bottom be available which includes parti-cle size distribution.
The output predictions of the oil-SPM interaction(s) and depositionmodel will ultimately need to be coupled to a set of oil slick trajectories.The result of these interactions is a "footprint" of oiled sediment on theocean bottom. This "footprint" will be characterized by concentration contours(gms oil/gms sediment) and depth of oil accumulation.
In summary, a specific ocean circulation model must (ultimately) beused to describe oil-SPM interactions and fates because of the following:
o Both vertical and horizontal transport are to be considered
o Specific weather must be used because weather determines or drivescirculation for specific sites and weather determines some of the en-vironmental parameters.
o Circulation is the determining variable for transport and resuspen-sion, position of oil inputs, and is essentially the INTEGRATOR thatbrings the model together.
1. 2.1 Dispersion of Oil Droplets
The dispersion of oil droplets into the water column is not a well-understood process. Yet, to predict the collision and result of a collisionbetween oil droplets and suspended particulates, the rate of input (i.e., dis-persion rate) of oil droplets into the water must be known along with the drop-let number concentration (not just oil concentration in mg/l). To date, pre-diction' of the dispersion rate is based (mostly) on empirical models which arelumped-parameter models. No model based on a "statistical-mechanical approach"for dispersion-rate prediction has ever been presented which is usable. There-fore, the prediction of oil droplet and suspended particulate interactions mustbegin with a review of the prediction of the source of one of the reacting com-ponents, i.e., oil droplets. The dispersion of oil droplets forms an
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oil-in-water emulsion, the properties of which are fairly well known. In orderto provide a source of oil droplets for the oil-SPM collision process, thisemulsion must be relatively stable.
As discussed in the following sections, turbulence alone cannot ac-count for the observed oil droplet sizes. The thermodynamics of the oil-in-water interaction may be the chief driving force for the production of the ma-jority of droplets, with turbulence and the presence of suspended particulatematerial affecting oil-SPM interaction rates.
Turbulence
Turbulence must be considered for an oil-spm kinetics model for tworeasons: the turbulent energy dissipation rate appears as a coefficient in thepanticle-particle collision expression, and turbulence is supected as determin-ing (in part) the oil-droplet-size distribution. "Turbulence" as a topic initself is an on-going research topic. It is the intent of the following dis-cussion to summarize information on "turbulence" with sufficient reference towhat is known and can be used in an oil-spm kinetic expression.
The most common models of oil dispersion are based on the turbulentbreakup of the oil where the turbulent energy is supplied by breaking waves(Raj, 1977; Milgram, 1978; Shonting, 1979). The breaking waves "beat" the oilinto the water column where a fraction of the "injected" oil remains as dis-persed droplets and the rest returns to the surface slick. These models havebeen developed relating turbulent energy dissipation rates (e) to sea state,especially wind speed. Sea state is a parameter also used to calculate the oilconcentration in the water column. Difficulties encountered with this methodof modeling oil droplet size and production rate using turbulence alone includethe lack of data on observed energy dissipation rates and the lack of correla-tion of theoretical oil concentrations and droplet sizes with observed values.
Table 1-3 lists energy dissipation rates measured in the ocean. Emphasis hasprimarily been on deep ocean measurements and not at the surface (0-2 m) orocean floor. The ocean surface has been estimated to have turbulent energy
1-17
Table 1-3. Observed Energy Dissipation Rates
Depth ( m) 3 Referencese(ergs/em /see)1 6.4 E-2 Liu (1985)
1-2 3.0 E-2 Stewart.& Grant (1962)15 3.0 E-2 Stewart & Grant (1962)15 2.5 E-2 Grant et a1. (1968)15 1.0 E-2 Liu (1985)27 5.2 E-3 Grant et a1. (1968)36 1.5 E-1 Be1yaev (1975)*40 2.65 E-3 Liu (1985)43 3.0 E-3 Grant et a1. (1968)58 4.8 E-3 Grant et a1. (1968)73 1.9 E-3 Grant et a1. (1968)89 3.4 E-4 Grant et a1. (1968)90 3.1 E-4 Grant et al. (1968)
100 6.25 E-4 Liu (1985)140 3.7 E-2 Be1yaev (1975)*
*In Raj (1977).
Unit C~nversions'3 2 31 erg/em sec - 1 em /see water
-4= 10 watts/kg water-7 3= 10 watts/em
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dissipation rates of 30 cm2/sec3 or higher in the top 6 cm with winds of 10 m/sec (Lin, 1978). Raj (1977) found that wind speeds of 12 m/s (25 knots) wouldbe required to suspend oil to a depth of two meters using only turbulence asthe dispersion process.
The air-sea boundary and sea-bottom boundary are expected to be theregions of greatest energy dissipation based on velocity profile considera-tions. Oil-droplet concentrations will be highest near the surface (near theslick) and sediment concentrations will be highest near the bottom (in resus-pension cases). The region of greatest oil-SMP interaction may then be themiddle region of lowest energy dissipation, with source terms of oil-dropletand sediment input described by the boundary regions (surface and bottom) ofhigher energy dissipation rates. Turbulent energy dissipation rates, whenknown, can be readily duplicated in the laboratory as discussed in the sectionon experimental procedures, though only with serious scaling uncertainties.
The prediction of oil droplet size from turbulence-only models gen-erally uses the Weber number approach. Milgram (1978) predicted that thesmallest droplet possible is approximately 50 ~m (while the typical dropletsize is larger). Aravamuden (1981) found a similar value but found an inverselinear relationship between droplet diameter and the number of droplets.Observations around an oil spill support this inverse relationship but theminimum observed droplet size was approximately 1 .~m (Shaw, 1977). The use ofthe Weber number approach also requires the predication of oil viscosity andoil-water interfacial surface tension over time. Neither of these physicalproperties is predictable strictly from oil composition.
\ The affect of turbulence on a coagulating suspension is complex. Hunt(1982) described this effect as two-fold. "First, it (turbulence) generatessmall-scale fluid shear which controls the suspended particle volume removalrate and second, disperses the discharged particle suspension which decreasethe particle concentration and lowers collision and removal rates."
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Emulsions
It is known from emulsion theory that without the presence of an emul-sifying agent, oil-in-water emulsions (for pure compounds) are limited to amaximum concentration of about 2% and are not stable (Clayton, 1923). Liquid-liquid emulsions may be stabilized by the addition of one of three types ofcompounds: 1) compounds with a polar-nonpolar structure (surfactants); 2)compounds which form a protective barrier at the liquid-liquid interface (hy-drophilic colloids, i.e., gelatins and gums); and 3) finely divided powders orinsoluble particles (Huang and Elliot, 1977; Overbeek, 1952). The use of agi-tation (turbulence) alone cannot result in the formation of a stableoil-in-water emulsion but increases the interaction rate of droplets with thestabilizing compound.
Stable oil-in-water emulsions may be formed spontaneously (i.e., wi~hno agitation) when polar compounds are present in the oil (Overbeek, 1952).Micelles are spontaneously formed by the alignment of the polar compounds intoa sphere with the hydrophilic heads at the water interface and the hydrophobictails to the center where the nonpolar oil compounds are contained. Thisalignment of polar-nonpolar hydrocarbons occurs in many biological systems andis the basis for the formation of cell membranes and the micelles that compriselatex and milk (Overbeek, 1952; Bretscher, 1985).
Oil-in-water emulsions formed either spontaneously or with astabiliz-ing agent have droplet sizes on the order of O.l~m for pure substances withsizes increasing for nonpure compounds and in the presence of electrolytes.Oil droplets have been experimentally produced in seawater (as an unstableemulsion) with agitation in this size range as measured by filtration (Shaw,1977).
Because oil is known to oxidize at ambient temperatures over time andits surface tension decreases (Payne et al., 1984, Payne and Phillips 1985), itis possible to hypothesize that polar products are formed in oil as it weathers(Baldwin and Daniel, 1953). This would lead to the increased possibility ofspontaneous emulsion formation and/or stabilized emulsion formation. The exact
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mechanism of oil-droplet formation probably involves the combined effects ofturbulence, spontaneous emulsification and increased stabilization due to polarcompound production and the presence of fine particles of suspended materials.
1.2.2 Sediment Transport
Sediment transport pertains to three specific topics: suspended sedi-ment, sediment resuspension, and sediment inventory on the bottom. In order towrite an oil and suspended particulate matter interaction model, the concentra-tion of suspended sediment that might interact with oil in the water columnmust be known. Therefore, the "add-on" calculation for the circulation modelis a sediment material balance for both the water column and the bottom.Therefore, it is necessary to address the modeling of sediment transport withrespect to the differential volume element shown in Figure 1-2. The derivedmathematical equations must be in a form valid for any water-phase concentra-tion species. Thus, the mass transport equations for sediment in the watercolumn will look the same as the equations for oil either as droplets or dis-solved species.
The concentration of suspended sediment in the water column can beconsidered as resulting from advection and mixing within the water body and re-suspension from the bottom. The former is part of the full three dimensionalnumerical circulation model of the water body and will include source boundaryconditions such as riverine input and coastal erosion. The latter involves asub-model of the bottom boundary layer which will provide bottom boundary con-ditions for the suspended sediment continuity equation and bottom friction co-effici~nts for the sea bed to the bottom boundary layer or suspended sedimentconcent~ations in the boundary layer resulting from resuspension (see Sections4 and 5). The incorporation of this bottom boundary condition into the 3-Dcirculation model can necessarily only be performed by the circulation model.
The suspended sediment, bottom boundary layer sub-model (described indetail in Section 5) is based on Grant and Madsen (1979, 1982) and Grant andGlenn (1983). The sub-model calculates the non-linear dynamics of surface waveand current interactions in frictional bottom boundary layers. The calculated
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bottom shear stress from this model (which includes moveable bed and stratifi-cation effects) is then related to sediment resuspension and transport throughthe Shields parameter. Inputs to this sub-model include:
1. Low frequency' surface wave characteristics (amplitude, frequency anddirection of the wave "which most feels the bottom - that is not neces-sarily the most significant wave; low frequency swells resuspend sedi-ment more easily than a steep choppy sea.)
2. Low frequency current and density profiles (from the 3-D circulationmodel). There is feedback from the boundary layer sub-model to thecurrent profiles and eddy viscosity parameters.
3. Bottom sediment characteristics, including size distribution and bedform characteristics.
currentThe theoretical mean current shear velocities calculated by all wavemodels developed to date generate values relatively close to those
have been determined from field measurements (Wiberg and Smith, 1983).and Smith (1983) used models originally developed by the late Dr.
whichWibergWilliam Grant to calculate the combined effects of waves and currents to pre-dict near bottom velocity profiles and values of boundary shear stress thatagreed reasonably well with reanalyzed data collected by Cacchione and Drake(1982). As discussed in detail in Sections 4 and 5, the results for two dif-ferent forms of the eddy viscosity indicated a significant enhancement of theboundary sheer velocity due to the current and waves compared to the slope ofthe velocity profile above the wave boundary layer due to the current only.Thus, models which incorporate wave behavior as well as currents provide a muchbetter estimate of the measure of sheer velocity than that which can be obtain-ed when only the currents are included in the calculations. In the evaluationof suspended particulate material migration, and in constructing an oil/SPM in-teraction model in general, it will be necessary to account for the presence ofwaves on the surface when estimating bottom stresses either from field data ortheoretically. Estimates of sediment transport rates that ignore the interac-tions of waves with currents will almost certainly be too low (Wiberg andSmith, 1983; Glen, 1983; and Grant and Glen 1983).
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1. 2.3 Interaction of Crude Oil with Suspended Particulate Material
Interactions of oil in the water column with suspended particulate ma-terial can occur by two different mechanisms. The first mechanism is on amolecular scale with dissolved oil species sorbing from the water phase ontothe suspended solids. The second mechanism is on a macroscopic scale with dis-persed drops of oil colliding with the suspended solids. The resulting loadedparticulates are ultimately deposited on the sea floor.
The interaction of oil with suspended particulates involves a numberof mass transport processes, illustrated in Figure 1-3, which are dependent onthe source terms for oil and sediment. The oil source term can be dissolutionof molecular species or dispersion of drops of oil from the parent slick, andthe dispersion process can be wind-induced turbulence or spontaneous emulsifi-cation (labeled 1-3, respectively, in Figure 1-3). The sediment source termoccurs as the result of turbulence at the ocean floor (path 6). Another signi-ficant sediment source term in Norton Sound is the Yukon River input. The in-teraction of oil and suspended particles in the water column occurs by sorptionof molecularly dissolved species (path 8), spontaneously dispersed drops col-liding with suspended particles (path 11), and as turbulence dispersed dropsalso colliding with particles (path 7). The sediment returns to the sea floor(path 9) with sorbed oil or associated with oil drops, or with no oil. Oil canalso transport to the sea floor as unassociated drops (path 4) or as dissolvedspecies (path 5). The transport of unassociated drops and molecular specieswill occur when there is little or "no" suspended sediment or when thereaction, i.e., sticking or adsorption, does not occur at an appreciable raterelative to be transport rate. Once oil is on the sea floor, it can be furthermixed into the deposited sediments by turnover mechanisms (path 10).
The mathematical description of the interaction of oil in the watercolumn with suspended particulate matter requires both thermodynamic and kine-tic information. The kinetic information must describe the strength of the oilsource terms (rates), the transport (movement) of oil and sediment in the watercolumn due to the local turbulent diffusivity, and the suspension deposition
1-23
OIL S LIe K
DISPERSIONFROMAGITATION
•DiSPeRSIONFROM SPONTANeous
_.-.- EMU LSI FICA TION
DISSOLUTION
-
seDIMENTATION
(!) CDNATURALDIFFUSION0'DISSOLveDSPICIIS
o (!)NATURALDIFFUSION 0'OIL "PARTICLES"
SEDIMeNT,FROM TURBLENCE
- -J seDIMENT TURNoveRAND COMPONENTDI"USION THROUGH ®SEDIMENT
Figure 1-3. Illustrations of possible oi1/SPM interactionsshowing transport and reaction paths. (Payne. et a1 •• 1984)
1-24
rates of sediment on the sea floor. The thermodynamic information mustdescribe the phase equilibrium of the molecular species for the water solidsorption. The sorption phenomena can conceptually be described the same waythat vapor-liquid distributions are described by Henry's Law. Usually, for thecase of dissolved hydrocarbons in the water column, the sorption ratio whichrelates the dissolved species concentration is a constant for very low concen-trations. Also to be considered is the oil water equilibrium of dissolvingspecies; this equilibrium has been described extensively in the open literatureas a partition coefficient, or M value.
Figure 1-3 is virtually applicable to the differential volume elementpresented in Figure 1-2. The oi1/SPM interactions are labeled numbers 7, 11,and 8, and the mathematical description of these interactions go "in" the dif-·ferentia1 volume element because they represent accumulation or change (whichcan be + or -) through reactions of species of interest. This is illustratedby considering dissolved compounds. The water column concentration of a hydro-carbon will change in the presence of sediment because of sorption processes.This change most likely will be described as an instantaneous reaction whichrequires that only a partition coefficient (thermodynamics) be used to describethis interaction. Of course, as the "plume" spreads the total concentration ofhydrocarbon decreases.
The input-output processes around numbers 7, 11 and 8 (i.e., all theother numbers) are essentially fluxes which describe the arrows in and out ofthe differential volume element in Figure 1-2. This is especially true at theboundaries of the air-sea and sea-floor interfaces. The near-shore zone ofshallow water is a special case of the sea-floor interface.
Therefore, in order to write the correct mathematical equations de-scribing oi1-SPM interactions it is necessary to be able to write a differen-tial material balance for oil and SPM. This procedure of writing the equationsyields the correct form of the mathematics to be used in the "add-on" calcula-tion to the circulation model.
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1.3 OIL/SPM INTERACTION MODEL DEVELOPMENT
The objective of the oil-droplet and suspended-particulate-matter in-teraction program is to quantify the reaction terms in the convection- diffu-sion equation for oil droplets and dissolved-oil species. The convective-diffusion equation is derived by writing a mass balance for the species ofinterest in a differential volume element. The result of writing the massbalance when three dimensions are considered yields the following partialdifferential equation for the concentration of species i:
ac. a a a1 + --(V C.) + --(V Ci) + --(V C.)
at ax x 1 ay y az z 1
(1-1)
a aCi a aCi a aCi--(k -)+--(k -)+--(k -)+R.x Y z 1ax ax ay ay az az
This partial differential equation is a mass balance which when integrated overtime and space yields the concentration of species i. This equation appears inall branches of science and engineering whenever a mass balance is written. Inthe above equation, the left-hand side, with the exception of (ac./at), repre-
1
sents advection through the differential volume element (which is fixed inspace) and the right-hand side, with the exception of R., describes horizontal
1
and vertical dispersion.
This partial differential equation is the basis for discussing and de-scribing oil and suspended-particulate-matter interactions in the water column.
above.the "interaction" information is contained in the reaction term R.
1
'This reaction term is a removal (output) or source (input) term for theAll of
species i. Thus, for oil-SPM interactions, it is necessary to describe whatspecies are going to be identified and kept track of. It is not possible toquantify every single species in the system; there are simply too many. In-stead, experience seems to indicate that simplifying assumptions can be made.
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The reaction for oil droplets in the water column describes the rateof 'collision and sticking of an oil droplet with a suspended particulate, i.e.,a loss of (free) oil droplet, and the settling (or rising) of an oil droplet.The reaction term Ri for oil droplets only then is
Rop K C Cop op p (1-2)
where K C C is the rate of collision and sticking of an oil droplet and aop op psuspended particulate to produce an oil-particulate agglomerate. The effect ofbuoyancy of oil droplets'or oil-SPM agglomerate appears in the vertical veloci-ty term in the partial differential equation (1-1).
Clearly, a mass balance must also be written for unoiled sediment.The partial differential equation for suspended sediment looks exactly the sameas that for Ci. Thus, in order to predict the interaction of oil and sedimentfor a specific location, a prediction of sediment transport is requiredapriori.
A complete list of the species of interest for oil-SPM interactionprediction includes: oil droplets as a function of size, sediment size and"type," and finally oil-particulate agglomerates. Oil-particulate agglomeratesrefer to oil-particulate species where the particulate is composed of one, two,three, ..., individual particulate(s), and the agglomerate is the result of oneoil droplet scavenging more than one particulate. There are an infinite numberof species when these types of agglomerates are considered. Since it is notpossible to keep track of all species even on the fastest computer (nor worth-while), some judgement based on existing results and experimentation must beused to either eliminate species or lump species into pseudocomponents.
An explicit requirement for an oil-SPM interaction and concentrationprediction is the velocity and dispersion vectors in the mass balance equation.It must be emphasized that these velocities and dispersion coefficients are notcalculated from an oil-SPM model. An oil-SPM transport model only uses these
1-27
parameters to calculate where the oil and SPM are transported. These para-meters come from an ocean circulation model, and if the ocean- circulationmodel computes salinity, then the ocean-circulation model can easily computeoil and SPM concentration in the same way (with appropriate boundary condi-tions).
In the discussion that follows a detailed statement of the oil andsuspended-particulate-matter interaction problem is given along with the sim-plifying assumptions that are being pursued. A review of the literature isthen given with emphasis on: particle-particle kinetics, the rate constant ofthese kinetics as a function of shear (and turbulence), oil droplets in water(emulsions), and the range of experimental parameters expected. Finally, inSection 2, a discussion of the results of the completed experiments is present-ed along with considerations on the utilization of these results and how theparameters are to be used in modeling.
1.3.1 Formal Description of Suspended Particulate Matter and Oil Interac-tions
The objective of the oil and suspended-particulate-matter interactionprogram is to describe the fate of oil in the water column when the presence ofsuspended particulate matter is considered. Oil exists in the water column asdiscrete droplets or (truly) dissolved oil species. The truly dissolved oilspecies can be either molecular specific species or pseudocomponents. The dis-solved oil species interact with the suspended particulate by adsorbing ontothe particle, while the oil droplets interact by colliding with and sticking tothe particulate. The adsorption of dissolved oil species by particulate isthought to affect no change in the particle's hydrodynamic characteristicswhile ~he oil-droplet particle species might affect a change in hydrodynamiccharacter relative to both parents.
An oil spill on the ocean surface moves as a function of environmentalconditions such as wind speed, waves, and water currents. As the slick weath-ers, dissolved species and droplets of oil are fluxed into the water column.
1-28
At the same time sediment transport occurs due (mainly) to a flux of sedimentto or from the bottom depending on wave conditions and currents. Thus, the twospecies, oil and particulate, interact and are transported due to the localvelocity and dispersion vectors.
The mathematics which describe the water column interactions are thecontinuity equations for the various species. In general, this equation is
aCi a a a+ --(V c.) + --(V c.) + --(V c.)
at ax x 1 ay y 1 az z 1
(1-3)
a ac. a ac. a ac.111--(k ---)+--(k ---)+--(k ---)+Rx Y z iax ax ay ay az az
where c. is the concentration of the ith species1
the velocityaction
of interest, t is time, V. are1
components, k.s are the dispersion components, and R. is the re-1 1
This equation can only be solved if the velocity and dispersionterm.components are known. Furthermore, when this equation applies to dilute spe-
the ofcoupled back to the hydrodynamic equations.
C. does not affect the bulk density of the1
fluid, or any
In other words ifcies, it is notpresence fluid, the (bulk)
viscosity of the other physical property of interest,on V and k while the converse is not true. For oil species,
c. depends1
C., in the water1
species are verycolumn, this "not coupled" assumption is applied because thedilute. This is apparently not the case for sediment at the bottom boundary.(See Sections 4 and 5). The continuity equation can be solved when V and k aregiven or specified as a function of x, y, z and time. If a circulation modelis available which computes these vectors and also salinity, then it isstraight forward to add the calculation procedure to consider other species.Actually, it is easier to add uncoupled species equations because (note that)salinity is coupled to the momentum equations through the bulk density. If thecontinuity equation for uncoupled species such as oil has to be integratedafter a circulation model is run, then a considerable amount of work must be
1-29
done to "write" an integration routine, parameterize the location of theboundary, and "plot" the results.
Consider now the reaction term for oil droplets. Oil droplets leave(change their identity) the water column by colliding with and sticking to sus-pended particulate. The rate expression for the "reaction" is postulated to be
R ,..K C Cop op 0 p (1-4)
where C is the oil-droplet concentration, C is the total particulate concen-o ptration, and K is the rate constant for this "reaction."opof turbulence or energy
Kopdissipation rate and is discussed in detail in the fol-
is a function
lowing section (1.3.2).
This interaction will result in a decrease in oil droplet concentra-tion, i.e., ac./at will decrease, so K C C is subtracted from the right hand~ op 0 pside of the continuity equation (1-3) for oil droplets.
When oil-droplet bouyancy is considered the continuity equation isfurther modified by the "rising" velocity according to
v = V' + WZ Z Z(1-5)
where V' is the z-component of the current velocity obtained from a (the) cir-zcu1ation model and W is the "rising" velocity. The above expression for V isz zto be used directly in the continuity equation for oil droplets.
The objective of this experimental program was to measure, verify, andgain insight on K C C. This work was conducted in a stirred-tank "reactor"op 0 p(see Sections 2.2 and 2.4).
Now consider the(at
suspended particulate matter in the water column.least) to consider: unoi1ed particulate, C ,andpu
The continuity equation for unoi1ed particulate alsoThereoiled
are two typesparticulate, Cpo
1-30
contains a loss term due to collision with and adherence to oil droplets.Thus, the reaction term for unoiled particles is
Ropu K C Copu 0 pu (1-6)
which is to be subtracted from the right hand side of the continuity equationfor unoiled particulate. The settling velocity for particulate must also beincluded in the V term for particulate only. Denoting the particle settlingzvelocity as U , the z-velocity component becomesz
Vz V' - Uz z (1-7)
where now a minus sign is used to denote the -z direction (settling toward thebottom).
At this point in the discussion, it should be apparent that keepingtrack of all kinds of species may well be impossible, especially if particulatesize fractions are to be considered. However, it is only necessary to keeptrack of those "things" which behave differently. An example of importancewhich now should be considered is oiled versus unoiled particles. If the set-tling velocity of these two species is not appreciably different, then there isno need to consider them as separate species. The important consideration thenis "appreciably different" when considered in the ocean environment. Sincesettling velocity is the "comparison", information on differential settlingmust be obtained by examining real ocean sediment to determine how sedimentsare size fractionated to the bottom. If it turns out that sediments with asettling velocity range of say 10% are uniformly deposited and experiments inthe laboratory show that oiled versus unoiled particulate fall in this range,then there is no need to consider separate particle species. Observation ap-pears, in a preliminary sense, to bear out the above postulate based on labora-tory data only, i.e., in the absence of floculation the observed settling ratesdiffer very little (see Section 6.1, Payne et al. 1984, and Section 3.2.1, ofthis report).
1-31
The continuity equations can be integrated only when boundary condi-tions are applied. For the case of oil droplets, the rate of dispersion pro-vides a "flux" boundary condition for this species at the ocean surface. Theboundary condition for this species at the bottom has not been discussed. Twopossibilities are dC /dz 0 at the bottom, i.e., no transport across theobottom; or C 0, i.e., the oil drops stick to the bottom. If sediment isobeing "lifted" from the bottom due to wave action, dC /dz = 0 would (probably)obe satisfactory.
1. 3.2 Detailed Discussion of Oil-SPM Kinetics
The rate of oil and SPM interaction, which appears as R. in the con-i.
tinuity equations, is written as
Rop K C Cop 0 p (1-8)
This equation is based on numerous research papers that have been published onthe general topic of the collision frequency of particles in a fluid medium.Therefore, in order to show why this equation can be used to describe oil-SPMinteractions, an abbreviated derivation is presented which also discusses howthis equation is adapted to a turbulent medium.
In order for oil droplets and SPM to interact, they must collide.Once they have collided, they can "stick" to form an oil-SPM agglomerate or re-bound to remain the same as before the collision. Therefore, the first step indescribing the oil-SPM interaction is to describe the collision frequency of(suspended) particles in a turbulent medium.
Consider a reference frame (x, y, z) centered on a particle which isfixed in space as shown in Figure 1-4. The fluid moves past the sphere in lam-inar flow where the velocity in the x-direction is given by U = -Gy. Thus, thevelocity is a function only of y and the sphere is transparent with respect tothe flowing fluid. If the sphere was not transparent, then the flow of fluidaround (rather than through) the sphere would have to be considered.
1-32
z
differential areaexposed to fluidvelocity
-"---+-\-++-----T~X
y
Figure 1-4. "Collision" Sphere of Radius at which denotes the collisiongeometry for monodispersed spheres of diameter a. Note thata "collision" sphere is the center-to-center distance ofapproach that results in contact. The projected differentialarea onto the yz plane (normal) is to be integrated over theplane weighted by the local velocity.
1-33
The objective of the derivation is to calculate the number of spheresmoving at the local fluid velocity that collide with the single sphere at theorigin. Thus, it is necessary to calculate the product of the local fluidvelocity (since the particles ride at this velocity) and the projected area ofthe sphere exposed to the local velocity. This concept can be visualized byexamining Figure 1-4. Note that the velocity is zero on or near the x-axis andthe projected area of the sphere in the region of the x axis is relativelylarge. Thus, there are relatively few collisions on the x-axis because theflow is small in this region. As the position of a flowing particle is movedoff the x-axis, its fluid velocity toward the target sphere goes up and sincethe projected area of the target sphere is finite, collisions can occur. As theposition of the moving particle changes towards y = radius of the targetsphere, note that the velocity is quite high which results in more particlesflowing through this position, but the projected area of the target sphere isalmost zero. Thus relatively few spheres collide in this region. Mathemati-cally, the above description is worked out as follows. A differential area ofthe surface of a sphere ~f radius "a" projected onto the y-z plane is
dA (sinO(a sin Od~)} (sin~(a dO)} (1-9)
or
(1-10)
any position y can be expressed as a function of a, 0 and ~ as
y = a sinO cos~ (1-11)
Therefore, the number of particle centers passing through a sphere of radius"a" about the origin is
nudA
n{G'a'sinOcos~}{a2sin20sin~dOd~}
nGa3sin30sin~cos~dOd~
(1-12)
where n is the number concentration of particles in the moving fluid. This isthe differential collision frequency of the particles in the moving fluid with
1-34
the single particle at the origin. Integrating 0 and ~ both through 0 to ~/2
for the upper octant and multiplying by 4 to get the entire "face" exposed tothe moving fluid yields
f 4 33 nGa (1-13)
The above expression is the collision frequency for the particles in the fluidwith the single particle fixed at the origin. To get the collision frequencyfor all the particles multiply f by n and then divide by 2. The division by 2must be made because otherwise the collision of i onto j and j onto i would becounted twice. Therefore, the collision frequency for a fluid containing nparticles with radius "a" per unit volume in laminar shear at G sec-l is
F 2 3 2G3 a n (1-14)
This equation is rearranged by taking into account of the volume concentrationof solids, which is
(1-15)
which when substituted into the collision-frequency equation yields
F4 ncG (1-16)
This is the typical equation for describing the particle-particle collisionfrequency for a system of monodispersed particles (Manley and Mason, 1952).Note that it is first order with respect to the particle concentration becausethe volume concentration of solids is constant. This equation has been testedin many experiments and shown to be valid. This equation applies to oil-oildroplet and particle-particle interactions to a first approximation.
1-35
In order to apply the collision frequency equation to oil-particle in-teractions, the identity of two different particles must be taken into consid-eration. The collision frequency of two different particles is
F..~J
4G 33 (r. + r.) n.n.
~ J ~ J (1-17)
where r. is the radius of the i-th particle (Birkner and Morgan, 1968). Notei.
that the shear appears in exactly the same manner as it does for the collisionfrequency of monodispersed particles.
The material balance, or population balance, for oil and suspendedparticulate can now be written using the above collision frequency equation.For oil droplets, the differential material balance is
dno
-oF4G 3
-0 '--3 (r + r) n no pop (1-18)dt
where 0 is introduced as the "stability" constant. This constant takes intoaccount the efficiency of oil droplet and particle adherence, i.e., sticking(Huang, 1976). If the particles collide but do not stick, 0 ~ 0; at the otherextreme is Q = 1. The above equation is applied to the (free) oil droplet con-centration as
dnodt -kGn n
o p(1-19)
where now k lumps 0 and the radius function. Thus, experimental measurementsessentially determine a lumped reaction rate constant which is kG. Similar ex-pressions apply to unoi1ed sediment and an oil-particle agglomerate which isalso the rate of formation of the k-th particle composed of an i + j agglomer-ate. In order to apply the above equation to oil droplets, suspended particu-late matter and the resulting agglomerates, at least three species are
1-36
identified here. Because the material balances that are actually used incalculations involve concentrations of mass rather than populations, thedifferential material balances are rewritten as
(1-20)
wherek lumps all unknowns for the reaction.The above equation relates the collision frequency to the (laminar)
shear rate. In order to apply this to the problem of interest, a turbulentshear is required. Saffman and Turner (1956) present an analysis of the colli-sion frequency in turbulent shear which results in
G (1-21)
where f is the (turbulent) energy dissipation per unit mass per unit time and v
is the kinematic viscosity.
Thus, the working equation for the rate of loss of the i-th particlesdue to collisions and sticking with the j-th particle is
dn.~dt (1-22)
The assumptions involved in deriving the above equation clearly do notreflect reality exactly. The relation of laminar shear and turbulent shearthat is invoked requires assumptions. Clearly the particles to which the equa-tion is to be applied are not spheres. Furthermore, the particles are distri-buted over a range of sizes. However, the basic form of the above equation hasbeen shown to be applicable in many situations and was used and verified in theexperimental program.
1-37
2.0 EXPERIMENTAL MEASUREMENTS OF OIL-DROPLET AND SUSPENDED-PARTICULATE-MATTER KINETICS
In this section of the report, we describe experiments that were con-ducted at the NOAA Kasitsna Bay Laboratory to determine the oil-SPM interactionkinetics. A brief discussion is also presented on how these results scale tothe open ocean and how they can be used in conjunction with an ocean-circulation model to predict the spatial distribution of sedimented oil on theocean floor.
2.1 BACKGROUND
Particle kinetics has been extensively described in the open litera-ture. Essentially all of this literature can be traced back to the originalwork of Smoluchowski (1917). A more recent example of the application ofSmoluchowski can be found in the work by Birkner and Morgan (1968). The paperby Birkner and Morgan describes a flocculation kinetics experiment which isvery similar in many attributes to the oil·SPM experiment.
The collision frequency for dilute suspensions of particles can be ex-pressed as
R f 1/2 31.3 (-) (r.+r.) n.n.1/ 1 J 1J
(2-1)
when R is the collision frequency, f is the energy dissipation per unit mass(of fluid) per unit time (cm2/sec3), 1/ is the kinematic viscosity (cm2/sec), r.
1
is the radius of particles i present at a number'density of n., and likewise. 1
for particles j. This equation describes only the collision frequency andnothing is implied about the "sticking" of particles.
Clearly, the above equation cannot be applied directly to oil dropletsand (or) SPM. The obvious problem is that a distribution of particle sizes ex-ists in any real situation, and the above equation is written for a specific
2-1
size. The above equation has been verified because it is possible to obtainsuspensions of single-sized spheres (latex or polymer) and conduct mono-sizedparticle-particle kinetic experiments.
However, it is not possible to generate mono-sized oil droplets, andSPM from the ocean is definitely not single ~ized or spherical. Therefore, inorder to apply the above equation to the kinetics of oil droplet-SPM interac-tions, the following assumptions are made.
1. Oil droplets in a narrow size range will behave as a mono-sizedpopulation, and
2. SPM in a narrow size range will likewise behave as a mono-sizedpopulation.
The primary reasons for "lumping" oil-droplet and suspended particu-late sizes are practical. Certainly calculations can be done which considerdistributions, but thes~ would consume considerable effort. However, since thenet result is to provide bounded estimates of the transport of oil rather thanexact answers, a "lumping" of parameters is required. Lumping parameters iscommonly done to provide a single parameter for a population, i.e., a mean ver-sus all values. The question that then must be answered is whether the meanadequately describes the population. For the case of a true-boiling-point dis-tillation the mean temperature of the cut "turns out" to be sufficient to beused to describe vapor pressure. Thus, lumping particle diameters over somerange for the purpose of describing kinetics is assumed, but presently therange of diameters included in, for example, the 10 micron class is not known.Experiments will determine what averages and ranges are reasonable.
If the preceding two assumptions are valid, then the rate equation canbe rewritten as
Rf 1/21.3 (- ) kn.n .II ~ J
(2-2)
2-2
where now k "lumps" the unknown information about the particle sizes. This isthe same equation as Equation 1-22, but the factor 1.3 is removed from k. Thisequation still does not contain information about the "sticking together ofparticles. It is this "sticking" together of particles, i.e., the oil-SPM ag-glomerate, that is important. In order to "see" the oil-SPM agglomerate, somekind of "balance" (such as a material balance) must be derived which describesthe kinetics that occur.
For the experiments described here, it was (finally) decided to usethe free oil-droplet number density as a direct measure of the kinetics. Inorder to derive this mathematically, consider that the rate of loss of free oildroplets is directly proportional to the collision frequency and sticking ofoil droplets and SPM. Thus, the rate of loss of free oil droplets (or SPM) isless than (or equal to) the rate of collision between these two types of parti-cles.
Therefore, the working equation which can describe oil-droplet and SPMinteractions is
R 1.3(~)1/2 k C C/.I a 0 p (2-3)
where now Coconvenient
is the concentration of oil (droplets) in the water in mg/l (orany other is the concentration of SPM in the water inunits), C
Pmg/l, R is the rate of collision and sticking of oil droplets and SPM, and kais a "lumped" parameter that includes unknown information such as the "stick-ing" efficiency and the size dependency. Because R is the rate of loss of freeoil droplets, R has units of mg (oil)/(l ·sec) and the parameter ka must haveunits derived from:
mg(oil) 2 1/2 mg(oil) mg(spm)cm sec;;; k (2-4)
1 3 2 a 1 1sec sec cm
which yields the result that k has units of reciprocal SPM concentration.a
2-3
lI
Application of the oil-SPM kinetic equation can be carried out in anyvessel or flow situation where the independent variables can be controlled.The experimental method chosen and found to work satisfactorily here was awell-stirred vessel (with no inflow or outflow) with a known power inputthrough a propeller. This is exactly the experimental setup used by Birknerand Morgan (1968). The objective of the experiment then is to introduce oildroplets (of a narrow size range) and SPM (of a narrow size range) into a ves-sel (beaker) of (stirred) water and measure the free oil-droplet counts versustime. If the concentration of the SPM is constant, i.e., its number densitydoes not change, then
d Co ~ -k Co (2-5)
where k
dt
1.3 (e/v)1/2k Ca p
so that integration of the above yields
CIn -kt (2-6)
where CO is the initial oil droplet concentration at time = O. The experimen-o
tal data, which are the oil-droplet counts normalized to the initial count,should fallon a straight line on a semi-log plot versus time if the assump-tions are correct.
In order to conduct this experiment there can be no other processesoccurring which affect the oil droplets or SPM. If other processes are occur-ring, then the appropriate differential equation must be written and solvedalong with the above equation. Examples of other processes are SPM loss due tosettling, or SPM flocculation. Experience indicates that both of these pro-cesses can occur and must be avoided.
2-4
One of the most important parameters of the oil-SPM kinetics problemis the oil-droplet size (distribution). The existing open-ocean oil-weatheringcode contains an algorithm for dispersion of oil into the water column. How-ever, the motivation for development of the dispersion algorithm (by ProfessorMackay) was for a material balance (of oil) around the slick, not informationabout the oil leaving the slick. As a result, there are no acceptable modelswhich predict oil-droplet size from a dispersing slick. Some researchers usethe so-called Weber number approach which predicts oil droplets larger than 50microns in diameter for ocean conditions. But, observations indicate that oildroplets much smaller, down around 5-10 microns, are prevalent. The mechanismwhich generates these small oil droplets is not known. Thus, for the purposeof conducting oil-SPM kinetic experiments, a size (range) must be chosen, andfor this experimental work, 1-10 micron diameter oil droplets were used becauseexperimental evidence seems to indicate this size range can and does occur inthe ocean.
2.2 EXPERIMENTAL TECHNIQUES AND RESULTS
The experimental hardware consisted of the apparatus shown in Figures2-1 and 2-2. Seawater was filtered through a 0.4 micron filter and added tothe 4-liter vessel. The stirring motor was turned on and adjusted to maintainin suspension 53 ~m sieved (Jakolof) SPM. The motor speed was approximately400 rpm. The use of 53-micron sieved sediment is a "practice", which removesparticulates that will not stay in suspension with existing (and attainable)experimental turbulence levels. An important experimental criterion is thatall sediment stay suspended; otherwise, the analysis of experimental data wouldrequire the accounting of the loss of sediment from the stirred water versustime. At the same time, "natural" SPM with size distributions from 1-50 mi-crons have been extensively documented in Alaskan coastal waters (Baker, 1983).Chemical and physical characterization data for the Jakolof Bay SPM are pre-sented in Tables 1-1,1-2A and l-2B in Section 1.1.
oil, volume
were prepared with a Hamilton Beach Scovill 7-SpeedFinding the correct combination of blending speed, vol-
of water, and "handling" required some initial testing.Blender,ume of
Oil dropletsmodel 626-3.
2-5
Figure 2-1 Experimental Hardware Used to Determine OIl.SPMInteraction Kinetics •
Bearing Support(attached to anexternal structure)
...•-I I-
I -
,.--I ...•-.:
-I ...•----- •--
- -C .....•) ~- -
Variable Speed Motor
Centerless Shaft Coupling
.Two-bearing Vertical ShaftSupport
4 Liter Pyrex Beaker(KIMAX)
2-inch Diameter, 3-BladePropeller, VWR # 58958-244
2-6
Figure 2-2. Execution of 4-liter oil/SPM interaction experiment at the NOAAKasitsna Bay field laboratory. Time-series aliquots are beingremoved for total oil load and SPM determinations by microscopic,gravimetric and FID-GC analyses.
2-7
The "visualization" of the oil droplets and particulate matter (withand without oil droplets) was carried out with visual microscopy. It was dis-covered (earlier) that the oil droplets would rise, even though they were quitesmall (5-10 microns). Stokes law predicts a rising velocity (for 5 micron di-ameter) of about 0.0004 cm/sec or about 1.5 cm/hour in the absence of turbu-lence. -.
The oil droplet "recipe" was 750 ml of filtered seawater, 15 drops of crude oilfrom a disposable Pasteur pipet, blending at speed 6 (which was labeled"blend") for five seconds, turning off for five seconds, and then on at speed 6for five (more) seconds. The contents of the blender were allowed to stand forfive minutes and oil that floated to the surface was skimmed off with a kleen-ex. The "correct" recipe for producing oil droplets is detemined by the poduc-tion of 10-mic~on diameter droplets. The choice of the 10-micron diameter isbased on rather scanty evidencce because the actual "configuration" of oilleaving a slick has never been completely or correctly investigated. Thus, adecision was made based on the available data as noted at the end of Section2.1. This oil droplet "recipe" yielded a final solution with droplets that re-mained in suspension in the water column and did not coalesce into a surfaceslick during the course of the experiment. As with the SPM described above, animportant experiemntal criterion is that all oil droplets stay suspended duringthe experiment.
The experiment was then started (time = 0) by pouring the contents ofthe blender into the agitated 4-1iter vessel which contained the SPM. Sampleswere taken for total (gross) SPM and oil loading (i.e., total oil and totalSPM, not number density) at this time. Samples for microscopic examinationwere then taken every few minutes for up to 30 minutes.
Therefore, by constructing a counting chamber with cover slips as il-lustrated in Figure 2-3, the free oil droplets were easily seen and counted.The thickness of the water-oi1-SPM sample was approximately 0.4 millimeter.Thus, the free oil drops could traverse this vertical distance in 100 seconds,and all of the free oil drops were at the water/upper-cover-slip surface whilethe SPM and oil-SPM agglomerates sank to the slide surface. By focusing the
2-8
Figure 2-3 Microscope Slide Arrangement for Viewing Oil Droplets and SPM.
Sample of oil-SPM, 50 ~I,placed between ends, ·cap·added to form flat upper surfaceand prevent evaporation "
NI\0
Rectangular cover slipto form ·cap·
~--- Standard slide
Two # 2 cover slipsstacked at each end,held in place by surfacetension of water
Note: This drawing is not to scale
· '
microscope on these free oil drops, only the free oil drops were seen becausethe depth-of-field focus (or lack of) caused the SPM which settled to the bot-tom of this water column to be completely out of focus. By adjusting the mi-croscope focus downward (approximately 0.4 mm) the SPM and oil-SPM particlescould be seen with the free oil droplets completely out of focus (not seen!).Visual counting was then conducted. The microscope used was a KYOWA #590136with a lOx eyepiece and lOx objective. The eyepiece had a Whipple disk in-stalled in it to aid in field definition for particle counting.
The experimental results are presented in Tables 2-1 through 2-9 andFigures 2-4 through 2-6. The experimental conditions were such that the SPMconcentration (in terms of number density) was in great excess of the oil con-centration. With this experimental condition, equation 2-6 applies for thepurpose of data analysis. Hence, a plot of the logarithm of the relative con-centration of free oil doplet numbers versus time should yield a straight line.This plot is then a test of the hypothesis represented in equation 2-6. Ifsuch a plot of the data did not yield a straight line, then futher refinementsor adjustments of parameters to control the experiment would have been neces-sary. Figure 2-4 presents the major results, which are plots of the naturallogarithm of the free oil-droplet counts (normalized to the initial oil-dropletcount) for four experiments. The lines plotted are least squares fits up to 14minutes. After 15 minutes the data "bends upward" indicating a loss of the"linear" relations present in the early stages of interation.
Note th~t oil loading in the water column never directly enters intothe data analysis. All that is required for the oil data is relative popula-tion counts. Another requirement though is the necessity of observing enoughoil droplets (under the microscope) so that statistical results and countingtime can be optimized. Counts were also made of the total free SPM and themaximum number of oil drops on any SPM particle at each time interval. Four tofive randomly choosen fields were counted on each slide for free oil, free SPMand oil droplets on SPM. In order to complete the counting experiment, approx-imately 3 hours at the microscope was required. A photographic recording pro-cedure was not perfected for this project. As a note of record, the oil load-ing in these experiments was approximately 20 mg/l.
2-10
Table2-1 Thursday - November 6, 1986, 11:20 a.m,OIL-SPMHalf Field
NII-'I-'
COUNT 1 COUNT 2 COUNT 3 COUNT 4TIME
OIL TOTAL OIL ON MAX Oil TOTAL Oil ON MAX Oil TOTAL Oil ON MAX Oil TOTAL Oil ON MAXMINUTES SPM SPM on, SPM SPM Oil SPM SPM Oil SPM SPM OIL
91 63 60 55
0 12 34 0 12 28 0 11 35 0 17 37 0
2 17 38 0 24 33 5 1 14· 41 2 1 22 26 2 1
4 24 32 5 3 10 24 0 16 24 3 3 7 41 2 1
6 11 25 8 4 16 23 3 1 18 30 4 1 6 32 5 2
8 7 26 2 1 8 18 6 3 8 31 7 2 4 12 8 5
10 8 62 5 1 8 54 5 1 6 30 12 6 4 41 5 4
15 3 6 4 3 3 24 8 2 4 18 13 4 4 32 18 5
20 5 18 25 7 4 17 5 2 3 15 8 7 2 14 8 5
25 . . . . . . . . . - . . . . - .
L 30 o I 28 7 7 I 0 18 3 3 0 18 6 3 7 23 5 2
CHI SQUARE DA TA FRII;II; Oil HAlF-fi ElD CHI AlII DATA •.•..•' r rorl ft
TIME CHI TIME , CHIMINUTES COUNT 1 COUNT 2 COUNT 3 COUNT 4 SQUARE MINUTES COUNT 1 COUNT 2 COUNT 3 COUNT ., SQUARE
2.0 17 24 14 22 3.26 0.0 34 28 35 37 1.34
4.0 24 10 16 7 11.64 2.0 36 33 41 26 3.47
6.0 11 16 18 8 6.80 4.0 32 24 24 41 &50
8.0 7 8 8 4 2.31 6.0 25 23 30 32 1.83
10.0 8 8 30 4 33.52 8.0 26 18 31 12 8.36
15.0 3 3 4 4 0.28 10.0 52 54 30 41 8.33
20.0 5 4 3 2 1.43 15.0 6 24 19 32 17.52
30.0 0 0 0 7 21.00 20.0 18 17 15 14 0.63
30.0 28 18 19 23 3.36
-------------_ ..-~---
NII-'N
Teble2-2·hursdey. November6, 1886, 3:00 p.m.OIL· SPMHel' Field
COUNT 1 COUNT 2 COUNT 3 COUNT 4TIME
~~:~LOIL O~ MAX TOTAL OIL 0•• MAX TOTAL OIL ON ~~X T~J~L O:-P~~ ~~XMINUTES OIL '\lPIl nil OIL 9PII SPII OIL OIL SPM 9PII OIL
104 123 115 18,0 . . · · · . . · . . . · . . . ·1 12 73 0 · 14 47 0 · 10 52 0 · 11 42 0 ·2 • 42 0 · 10 40 2 1 10 31 0 · 7 30 0 ·3 10 17 7 4 · 27 0 · 11 13 4 2 15 81 2 1
4 3 81 2 1 · 51 1 1 • 72 11 2 • 57 3 1
5 7 41 1 2 11 51 3 1 12 52 7 1 . 41 5 2
8 3 47 1 1 • 55 5 1 • 47 0 0 4 75 8 2
• 5 41 7 1 8 43 • 2 4 " 43 • 4 30 8 32
10 2 40 7 2 8 12 8 2 3 21 • 3 1 25 7 4
15 2 ,. 7 1 0 22 7 2 3 41 15 4 1 50 14 8
20 0 1. 3 1 2 Ie 10 8 1 15 12 8 2 17 8 4
25 1 47 7 2 4 87 5 2 0 22 ,. • • ,. 2 2
30 2 17 4 2 · 18 11 3 1 ,. 7 1 4 24 • 2
CHI SQUARE DATA FOR FREE OIL CHI SQUARE DATA FOR IPM COUNTS
TIMECOUNT 1 COUNT : COUNT 3 COUNT 4
CHI TillECOUNT 1 COUNT 2 COUNT 3 COUNT •• CHI
MINUTES SQUARE MINUTES SQUARE
1.0 12 14 10 11 0.74 1.0 73 47 52 42 10.41
2.0 • 10 10 7 o.e7 2.0 42 40 31 30 2.27
3.0 10 11 15 · 1.17 3.0 37 27 13 81 20.28
4.0 3 • • · 3.10 4.0 11 51 72 57 2.18
5.0 7 11 12 · 1.40 5.0 41 51 52 41 1.17
8.0 3 • • 4 4.12 8.0 47 55 47 75 1.38
'.0 5 8 4 4 0.51 '.0 41 43 43 30 4.34
10.0 2 8 3 • 2.57 10.0 40 32 21 25 7.01
15.0 2 0 3 3 3.00 15.0 11 22 41 50 23.53
20.0 0 2 3 2 2.71 20.0 1. Ie 15 117 41.34
25.0 1 4 0 3 5.00 25.0 47 17 22 3 2.07
30.0 2 1 4 . - 30. 17 18 11 24 0.00
0,0 1 1 1 1
Table 2-3 Friday - November 7. 1986. 5:00 p.m.OIL-SPMFull Field
COUNT 1 COUNT 2 COUNT 3 COUNT 4TillE OIL TOTAL OIL ON IIAX OIL TOTAL OIL ON IIAX OIL TOTAL OIL ON IIAX OIL TOTAL OIL ON IIAXIIINUTES SPII SPII OIL SPII SPII OIL SPII SPII OIL SPII SPII OIL
1 24 62 0 0 16 112 0 0 20 113 1 1 15 129 2 13 21 115 3 1 13 149 4 1 10 114 8 3 23 154 8 2
5 - - - - - - - . - . . - . . - -7 23 109 8 2 11 79 9 3 8 108 7 2 12 119 8 2
9 7 109 11 3 8 141 18 3 8 102 22 8 8 129 20 3
11 8 114 8 1 18 123 11 3 "3 82 21 4 14 115 13 2
15 5 118 26 7 5 47 3 1 8 85 27 4 8 " 18 3
23 5 112 19 5 2 87 8 5 4 81 5 2 5 81 8 3
25 4 108 21 4 4 83 13 4 3 83 23 5 2 88 8 3
30 4 54 18 4 3 81 22 4 5 47 8 4 3 45 8 3
CHI SQUARE DATA FREE OIL CHI SQUARE DATA &PII DATA
TIMECOUNT ~
CHI TIMECOUNT 2 COUNT 3
CHIMINUTES COUNT 1 COUNT 2 COUNT 3 SQUARE MINUTES COUNT 1 COUNT 4 SQUARE
1.0 24 18 20 15 2.71 1.0 82 112 113 128 24.37
3.0 21 13 10 23 8.97 3.0 115 148 114 154 10.38
7.0 23 11 8 12 11.85 7.0 108 78 108 118 8.58
8.0 7 8 8 8 0.38 8.0 108 141 102 129 8.04
11.0 8 18 3 14 11.87 11.0 114 123 82 115 22.68
15.0 5 5 8 8 0.18 15.0 118 , 47 95 " 29.45
23.0 5 2 4 5 1.50 23.0 112 67 81 81 12.25
25.0 4 4 3 2 0.85 2510 108 83 83 88 10.99
30.0 4 3 5 3 0.73 30.0 54 61 47 45 3.07
~------------------_.
Tab182-4 Saturday - November 8, 1986, 10:45 8.m.OIL - SPY
Half Fleld*'Full Field
NI•....~
COUNT 1 COUNT 2 COUNT 3 COUNT 4
TIMEOIL TOTAL OIL ON MAX TOTAL OIL ON MAX TOTAL OIL ON MAX TOTAL OIL ON MAXOIL OIL OILMINUTES SPM SPM OIL SPM SPII OIL SPII SPM OIL SPM SPM OIL
74" 134" 155" 145"
1 22 91 5 1 20 92 1 1 32 129 4 3 34 123 4 1
3 17 103 7 2 24 93 5 2 18 110 13 2 15 112 10 2
5 13 8 1 1 15 28 2 1 22 104 6 2 13 88 14 4
7 20 89 7 2 21 123 13 4 16 112 16 4 23 130 24 5
8 6 125 22 4 13 51 6 2 4 27 1 1 13 73 11 3
11 13 71 18 3 6 47 8 3 8 82 11 5 10 86 18 5
15 5 67 15 15 7 67 15 4 7 63 8 2 8 62 16 4
20 10 43 23 5 8 34 22 9 7 64 5 2 11 66 28 6
25 4 75 24 7 3 64 24 6 8 82 28 5 5 ...- 33 8
30 4 63 31 6 3 34 14 3 7 25 11 3 4 35 12 3
CHI SQUARE DATA FREE OIL CHI SQUARE DATA FOR &PM COUNTS
TIME ~OUNT 1 COUNT 2 ~OUNT 3 COUNT 4 CHI TIME·COUNT 1 COUNT 4
CHIMINUTES SQUARE MINUTES COUNT 2 COUNT 3 SQUARE
1.0 22 20 32 34 5.48 1.0 81 92 128 123 11.11
3.0 . 24 18 15 17 2.43 3.0 103 83 110 112 2.11
5.0 13 15 22 13 3.48 5.0 8 28 104 88 112.23
7.0 20 21 16 23 1.30 7.0 89 123 112 130 8.50
8.0 6 13 4 13 7.33 8.0 125 51 27 73 75.94
11.0 6 9 10 13 2.63 11.0 71 47 82 98 17.38
15.0 5 7 7 9 1.14 15.0 67 67 63 62 0.32
20.0 10 8 7 11 1.11 20.0 43 34 64 68 14.39
25.0 4 3 9 5 3.95 25.0 75 64 82 44 12.45
30.0 •• 3 7 4 2.00 30.0 63 34 25 35 20.71
Table 2-5 Thursday· November 6, 1986, 10:50 a.m.011 Only
Full Field
TIME COUNT 1 COUNT 2 COUNT 3 COUNT 4 TOTAL CHIMINUTES SQUARE
0 24 34 39 36 133·. 3.812 23 30 25 33 111 2.264 29 41 33 35 138 2.176 37 37 39 28 141 2.068 39" 34 24 35 132 3.70
10 21 35 43 40 139 8.1912.5 43 31 29 31 134 3.67
15 40 33 35 31 139 1.29..
20 24 27 31 30 112 1.07
2-15
2-16
Table 2-6 Friday • November 7, 1986, 8:00 a.m.011 Only
Full Field
TIME COUNT 1 COUNT ~ COUNT 3 COUNT 4 CHIMINUTES SQUARE
0 10 13 6 15 4.182 15 12 13 7 2.964 8 11 8 15 3.146 7 9 5 8 1.218 8 7 2 4 4.33
10 11 9 11 10 0.2715 8 6 11 6 2.1620 4. 5 9 10 3.7125 9 4 6 8 2.1930 2 5 8 6 3.57
Table 2-7 Saturday· November 8, 1986, 3:20 p.m.Oil Only
Full Field
TIME COUNT 1 COUNT 2 COUNT 3 COUNT 4 COUNT 5 CHISQUARE
1 22 36 12 17 18 15.81. ,
3 19 23 21 24 28 2.005 24 24 27 27 22 0.767 19 22 28 24 19 2.559 17 14 20 10 20 4.49
11 22 19 26 20 19 1.6415 , 20 20 16 14 27 5.1120 13 15 24 16 28 8.6925 13 18 17 19 20 1.68~
30 17 21 23 25 15 3.41
2-17 III
II
J
Table2-B Oil/SPM Interaction and Sedimentation Experiments.
011/SP" Interaction and ~edl~ntatlon F.Kperl•• nt~Cravilletrtc SP" Load~ and ToulOn f:"tl_t"!1Kaattana Ray. AK---Nove.ber 19R6
~edtl'lentConcentrlltlon Tot. 011 Concentration~.p. (~/llter) FlO nC21 Tot. 011 Vol. ****S •.,le WelRhta (.-)****
~a.ple 'D rep. GC Cone. F.STIHATF. Flit. Filter FI Iter SedillentEllperl_nt ID Ileacrlptlon No. no. ~a.,le Hean Std.Dev. Elltr, (uR/I) (~/I) (.Ia) + Sed. Tare Wel_htJakolof Sed.-I No "eOll/DCN h02S.0 z:o 0.10320 0.01115 0.08605(Hothu Liquor) + HeOM/DOI 41022.0 X 5.0 0.22260 0.01749 0.20511•..•..•.•.••..... ........................... •.•.•.•.•.•.•.•..........••.. ....~~•.....•..•..••.•••. .....................................Jakolof Sed.-II No HeOM/DCN I 41601\.7 1.0 0.14296 0.01814 0.12482("other Liquor) 2 411120.0 41812.2 IR9.4 3.0 0.14421 0.01815 0.12546
3 42070.0 3.0 0.14400 0.01779 0.12621- - - - - ------ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
+ lteOM/DOt I 42220.0 3.0 0.14445 0.01779 0.126M2 42056.7 42157.8 72.1 3.0 0.14419 0.011102 0.126173 42196.7 3.0 0.14443 0.01784 0.12659••.••.••..•...•.. ..•........••..•..••••.•••• ..•.......................... .•.....•................. ...•....•.....•......................
N 5 Nov. 1986 Pre-oll TO 59.6 25 0.01952 0.011101 0.00149I (Kirstein/Clary) 10 .In + 011 T3 32.11 25 0.01877 0.01795 0.000112•....
00 (A") Final Rot. Sed. I 0.03055 0.011110 0.01225••.••.••......... ............••.•......•.••. ............................. ......................... .....................................6 Nov. 19116 Pre-oll TO flO. 1 I 0.19 75 0.022011 0.01756 0.00452
(Ittrsteln/Clary) o-l .In + all TI 42.1 I 26.73 23.9 75 0.02021 0.01705 0.00316(AH) Ifl-ill.In + all T2 4fl.0 X 30.97 27.7 75 0.02048 0.01703 0.OOl4,)
30-12 .In + oil T3 44.3 I III.]] Ifl.4 75 0.02232 0.01900 0.00312•.•...•.•........ .....•..•....•.......•..•.. •...•.•.••....•.......•.•••.• ..............•.....•.•.. .•...••........•.....................6 Nov. 19116 Pre-oll TO 52.7 X 0.411 75 0.02052 0.01657 0.00395
(KI rsteln/Clary) 1-3.5.1n + oil TI 44.0 I 111.75 16.8 75 0.02106 0.01776 O.OOllO(PH) 15-111 .In + oil T2 41.5 I 16.fl2 14.11 75 0.02055 0.01744 0.00111
lO-3l .1n + oil T3 41.3 I 11.7 10.5 75 0.02065 0.01740 0.00125.•••........•...• ............••...••.•..••.. .....•.•.....•••..•••.•...••. ...............•.. ~. .....................................7 Nov. 198fl Pre-oll TO 57.1 l( INC INC 75 0.02160 0.01730 0.004)0
(I(Irsteln/Clary) 1-1.5 .In + 011 TI 54.0 I INC INC 75 0.02246 0.01841 0.004055 PH Ellpt. 15-18 .In + all T2 46.0 I INC INC 75 0.02161 0.018111 0.00345
30-)) .In + all T3 SO.I I INC INC 75 0.02169 0~01791 0.00176.....•.......•... .....................•..... •...•.•...•...........•...•.. ......................... .....................................8 Nov. 1986 Pre-oll TO 1i0.0 I INC INC 75 0.02235 0.01785 0.00450
(1(1rateln/Clary) 1-).5 .In + all TI 47.6 I 26.11 2).1 75 0.02205 0.0111411 0.00)5711 Nt bpt. 15-18.1n + all T2 46.3 I 20.09 17.9 75 0.021611 0.01821 0.00347
10-1) .In + all T) 44.8 I INC INC 75 0.0204') 0.01709 0.003l6.....•.....•....• ...................•.•..... ..••...•..........•.......... .......•................. ••....•..•..••...•.•..•....•...••....
Table 2-9 Oil/SPM Interaction and Sedimentation Experiments.Otl/SPH Interaction and Sedl.entatlon F.xperlmentaGravl-etrlc SPH LoadA and Total 011 F.atl.atPAKaaltsna Bay, AK---NoveMber 1986
6 Nov, 1986Oiled
Sedl_ntatlonEllperl_nt
(Kirstein/Clary)( ....)
IWater Te••p.- 20.~ ci
NJI-'\0
I 28.22 2~.21 19.4- - - -I 21.82 16.21 16.0
SaMpleDescription
--SO--I-21
rep.no.
S~dl••nt Conrentratton("R/ltter)
Hean
~"1~.249.0
42.7
Std.Dev.
0.001410.001260.00097
o ••In Rettie
15 .In settle 515 I21
28.211.025.6
Tot. 011FillGCElltr,
ConcentrRtlnnnC21 Tot. 011Cnnr. ESTIHATF.
(uR/I) (~/l)
Vol. ····SaMple WelRhts (R.) ••••FUt. Filter Filtu Sedl_nt(••Is) + Sed. Tare Weljlht'5'0 0.01970 0.01751 0.00219
50 0.01926 0.01750 0.0017650 0.020n 0.018011 0.0024S- - - - - - - - - - - - - - -50 0.01812 0.01691 0.0014150 O.0194R n.01781 0.0016550 0.01960 0.01812 0.00128
15 .In settle 515
60 .In settle 560
110 .In sett Ie 5110 ISPH 2
1
110 .In sett Ie 5110 IBot. 2Sed. 1
24.1
8.420.8II.'"
1.1
- - - - - - - - - - - - - - - - - - - - - - - - - -50 0.n1979
1.7 50 0.0192050 0.01915
0.018180.017940.01818- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
18.050 0.01828 0.01719 0.00109
2.7 50 o.olno 0.011169 0.00011150 0.01875 0.01795 0.00080
- - - - - - - - - - - - - - - - - - - - - - - - - - - - -J[ 2.51 2.1 50 0.01790 0.01748 0.00042
~.1 J[ 1.21 2.9 50 0.01971 0.n11l67 0.00104J[ 1.95 1.~ 50 0.01766 0.01708 0.000~8- . - - - - - - - - - - - - - - - - - - - - - - - - - - -J[ 0.01199 0.01808 0.01l91J( 0.0J2~2 0.01747 0.01505J[ 0.0))57 0.01797 0.01560.....•........... .....••..............••.... ......................••....• .. .
7 Nov. 1986 0 .In stir CTO 50.8 50 0.02112 0.018~" 0.002~4Dnolled - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - _ - _ - - - - - -
Sedl_ntatlon 10 .In stir CT10 49.2 50 0.02008 0.01762 0.00246Ellperl_nt - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
IWater TeMP.- 20.~ CI
o .In settle CSO I21
52.251.251.2
52.2 n.1I0.020480.019680.01899
0.002610.002660.0025'
15 .In settle CSI~ I21
------- - - - - - - - - -'J5••In aett Ie CS15 I23
- - - - - - - - - - - - - - - -60.ln sett Ie CS60 I
23
1I01llinsert Ie CSIIO ISPH 2
1
0.017870.01702
.0.01641- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -54.6 50 0.02027 0.01754 0.0027141.4 45.5 6.7 ~O 0.01977 0.01760 0.0021718.6 ~O 0.02067 0.01874 0.00191- - - - - - - - - - - - - - - - - - - - - - - - - - - - - -24.2 50 0.01797 0.01676 0.001212~.2 26.9 1.2 50 0.011140 0.01714 0.0012631.4 50 0.01857 0.01700 0.00157
- - - - - - - - - - - - - - - - ------- - - - - - - - - - -10.6 50 0.01116/1 0.01815 0.00053n.ll ri.s 2.4 ')0 0.017"" 0.01700 0.0006816.6 ')0 0.01900 0.01817 0.000113
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -17.0 50 0.01840 0.01755 0.000/1')1/1.6 1';.2 1.7 'i0 0.0111')0 0.0111';7 0.0009110.0 ';0 0.01/169 0.01819 0.000';0-_ .........•.••.•.......•..•.......•••...•...•.•.•..••.......•.....•.•....•.......•..•.••..•..••....••.•.•••••••••.•..••.•.•...•.•...••
---------- --- ----------
-•en 2.5D-Oa:c
N •••I 0N0 ••••••a: 2.0II.
•III>~.5
1.5
SLOPES
1.30 E·1 • 11·6-86Thursda, 3:30 p.m.
1.50 E2 X 11•••86 Saturda, 10:45 a.m.
'.75 E·2 0 11-7'" Frida, 5:00 p.m.
3.5 " 1.1' ~-1 D 1
I '"~~
," I
~ '".... ~ ~h. ~
X
"" X, ~ r\.4 " 'X~ ~
"x " ~ ~II -; ." "-. "'Ii ...• ,&... IIli..
~ ~- ~ ,~ "'- I'.. X
X r... "- X
" "-" "' ,I
I\.. -;
-" X,
\ II.~
3.0
x
1.0o 10 25 30205 15
TIME (MIN.)
Figure 2-4 Oll-SPM Interactions Free 011Count·
• normalized to full field counts
-•0Do 3.00II:
N QI =NI-' 0
•••IIIII: 2.5II.
••III>C-oS
2.0
SLOPES
, 3.461 E·2 • 11-6-86 Thursda, 3:30 p.m.
'3.26 E2 X 11••-86 SIIturda, 10:45 a.m.
'\. 1.57 E·2 0 11·7-86 Frida, 5:00 p.m.
4.0
•.•.. t " .." •.•. •.•.•.'u' :.', , •.J ,•. "I' •....•. "
.'
•- .•..•. -. .•. -:-- -~:-. .•. .•. ..... .•. .•. .-•
~,
.X
"""" X X-~ ••••• -- ••••• ~•••• •••••• X
X •••• XX
X XI I I I
3.5
1.5
o 10 25 3015TIME (MIN.)
205
Figure 2-5 Oil Interactions (Oil Only).
e-(I)A. 5.00a:Q
N -'I 6NN IIJ
IIJa: 4.5II.
••••>4C-.54.0
SLOPES
"3.461 E·2 • 11·6-1&'"ursd., 3:30 p.m.
'3.26 E2 X 11·.·.. a.turd., 10:45•.m.
"1.57 E·2 0 11·7·.. Friel., 5:00 p.m.
'\. 2.3 1:20 •.m.
5.5
II
I•
••••••II•••r•:
~ ~.....t..,".•.. 1.0 .• ""
__ X
oil..- I •• ...• )...• .... •.., -=t .... ••# "I•••••• .... ...• •••••• Ilil. I••• ••••••• ~•: X r-.- ~
'"l
I
~ ~ r-.- I" X""-! - "• X :- ~• ~
r I'""'"' ~•• ••I
: II
••3.5o 10 20 30155 25
nME (MIN.)
Flgure2-6 Oll-SPM Interactions Total Free SPM.
• normalized to full field counts
From theequation (2-5) is k
data in Figure 2-4, the interaction constant described in-1 -1= 0.107 minutes or O.OOlS seconds ,which results in
e1.3 (-)1/2 kC
a p-1
= O.OOlS·sec (2 -7)11
From Tables 2-S and 2-9 the sediment loading was measured to be approximately4S mg/l, so that the above becomes
2.9 x 10-5 1mg. sec (2-S)
In order to attribute the decrease in oil-droplet number density tooil-SPM interactions, a "blank" experiment was conducted with no SPM present.These results are presented in Figure 2-5 and should yield straight lines withzero (no loss of oil droplets) slope indicating no oil-oil interaction. Thisappeared to be the case for two experiments while a third case yielded a slopeof -0.0157. This slope is still smaller than those in Figure 2-4 (when SPM waspresent) where the slopes ranged from -0.0875 to -0.13.
Thus, it is concluded from these "blank" experiments that oil dropletsdo not interact (collide and stick) at a rate that is comparable to the oil-SPMrate.
Counts were also made of SPM at each time step to determine if SPM wasflocculatingslope from
significantly. The results are shown in Figure 2-6. The averagethis graph is -0.11 indicating some flocculation is occurring, but
again, not as significantly as oil-SPM interactions.
Tables 2-1 through 2-7 present the actual counting data obtained. Thevolume counted for each experiment was 50 ~l so that the results are directlycomparable on a volumetric basis. Some variation occurred in oil and SPMload-ing (Tables 2-S and 2-9) but this variation will not affect the development ofa rate term. Chi square tests of the data indicate that more counts should be
2-23
made in the future to insure statistical confidence. This will not be a prob-lem (in terms of time needed per experiment) as it will not be necessary tocount SPM or oil-SPM agglomerates.
The determination of the power input to the propeller (and hence theenergy per unit time dissipated) was measured with the experimental hardwareshown in Figures 2-7 and 2-8. A string was wound onto the stirring shaft (mo-tor removed) and a weight attached. The (falling) mass (or weight) was thenadjusted so that the shaft would rotate at the same speed at which it was driv-en during an experiment. This matching of speeds is crucial because the powerrequired to drive the propeller is proportional to rate of rotation. The shaftrotation rate was measured electronically (Figures 2-8 through 2-10). Once therotation rate had been established by adjusting the weight, the time requiredfor the weight to fall a known distance at constant velocity was measured.From this information the power is calculated from
P = mgh/t (2-9)
where the term mgh is the change in potential energy (in a gravity field). Thesame measurements were then taken with no water in the vessel so that the ener-gy dissipation due to bearing friction could be subtracted. The net mass re-quired to stir the vessel at 400 rpm was found to be 68 grams and the distancetraversed was 2 feet (61 cm) in 4.5 seconds. Thus
2(68 grams) (980 cm/sec )(61 cm)P (2-10)
4.5 sec
p5 dynes'cm
9.03 x 10 (2-11)sec
For a liquid volume of 3500 ml and density of 1 gm/cc,
€ =
9.03 x 105 gm'cm2/sec3
3 3(3500 cm )(1 gm/cm )
2cm258 3sec
(2-12)
2-24
Figure2-7 experimental Hardware to Measure the PowerDissipated In a Stirred Vessel.
Bearing SupportTwo-bearing Vertical ShaftSupport
I----:~:::;-:.,..----__r""""._ Roller bearingexternally supported
• String (6# test)
)4-10-- 2-inch diameter, 3-Blade-- propeller, VWR # 58958-244
Note: The string is wound "up" on the shaft, the falling weight allowed to reachconstant velocity, and the time required to traverse a vertical distancerecorded.Power dissipated:= ~9h
Ime
2-25
Figure 2-8. Determination of weight required to achieve 400 rpm stirringturbulence in the 4-liter beaker experiments. Note that thestirring motor is de-coupled from the propeller shaft during thefalling weight drop timed experiment. Additional studies werecompleted without water in the beaker to quantify the effects offriction in determining the power input to the stirred chambersystem.
2-26
Figure 2-9. Construction ofrately measureexperiments.
the binary counting circuit board used to accu-rpm in the 4-1iter beaker oil/SPM interaction
2-27
Figure 2-10. Trigger mechanism attached to the stirrer shaft and binary count-ing circuit board (in the background adjacent to the batterypower supply) for the experimental rpm determinations.
2-28
160 -1sec (2-13)
and finally
2 3258 cm /sec( 2)0.01 cm /sec
1/2
Using this value of (f/v)1/2 results in
5 12.9 x 10k mg. sec (2-14)a 160 sec -1
or
k 1.8 x 10-7 1- (2-15)a mg
This value of k then.represents the term shown in equation 2-3. It is validafor the size range of particles used in its experimental determination andshould not be extrapolated to other particle sizes. Extrapolation to othernumber densities is valid, as is extrapolation to other f/V values.
From these expriments it can be concluded that oil droplets and SPM docollide and stick in a turbulent field. It must be emphasized that these ex-periments were conducted with fresh (unweathered) Prudhoe Bay crude and Jakolofsediment. Only one set of experimental conditions was (repeatedly) investigat-ed. Extrapolation to other oils, weathered Prudhoe Bay oil and other sedimentsis not valid. These experiments present a successful observation of oil-SPMinteraction kinetics and a measured rate constant under rigorously controlledexperimental conditions.
The application of the results measured in these oil-SPM experimentsbegins with the equation of continuity for free oil droplets.
2-29
(2-16)
a C a a aat 0 + ax(VxCo) + ay(VyCo) + az(VzCo)
a ac a ac a ac000ax(kx ax )+ay(kyay ) + az(kz a;-) + Rop
The determination of the velocity and turbulent tran~port coefficientsand resulting integrationcirculation model. The
of this equation must be accomplished by an oceanoil-SPM kinetic expression is R above and thus de-
scribes the rate of loss of free oil droplets in the water column (and also theproduction rate for oil-SPM agglomerates). R is equation 2-3 (with a - sign).This continuity equation (in the water column) requires boundary conditions forboth sediment and oil droplets.
2.3 IMPLICATIONS FOR MODEL DEVELOPMENT
2.3.1 Application of .Oil-SPM Kinetic Equations
The application of kinetic equations for particle-particle interac-tions involves some subtleties which can best be illustrated with an example.The concept that will be illustrated in this example is that of the relation-ship between "concentration" and "number density" and how this concept appliesto the assumptions made for the Kasitsna Bay experiments conducted in November1986. Note that the rate equation (and the working equation for the Novemberexperiments) for the free oil-drop concentration contains the sediment "concen-tration, II i.e. ,
dCo (2-17)dt
Based on observations over time frames much longer than those for the Novemberexperiments (i.e., longer than 30 minutes), it was noted that the SPM doesflocculate. This means that the SPM concentration as related to number densityof SPM particles changes with respect to time. Using a constant value for Cpthen is not strictly correct. To be correct, the value of C in the above rate
p
2-30
equation must decrease with time even though the actual SPM concentration interms of mg/l is constant (i.e., no distinction if there are many small parti-cles or a few large ones in suspension).
Therefore, consider how C could be corrected for the short timeframep
of the experiments if the loss of SPM "numbers" is an experimental objective.The starting point for SPM-SPM kinetic description is the SPM collision fre-quency equation:
R (2-18)
where nl is the number density of singlets, i.e.• fresh suspended particles.This equation is the rate at which SPM particles collide with themselves, notoil drops. Now assume that every collision results in sticking to form the"doublet" as follows:
This equation describes the stoichiometry of the particles. Using this equa-tion the rate of loss of singlets is
2-2k ns 1 (2-20)
because every collision results in the loss of two particles. The rate of ap-pearance of doublets is
(2-21)
This assumes (for the sake of illustration and simplicity) that the "doublets"do not react with anything. However, a similar equation for the collision andsticking of doublets to form higher order particles can (in principle) be
2-31
written. Solving the above equation for nl with nOl particles present at t=O
yields
Note that the "material balance" or stoichiometry is preserved, i.e.,
(2-23)and as t --> ~, the result for n2 becomes
(2-24)
But, observing this result experimentally cannot be done using "concentration"of SPM, i.e., the concentration of SPM is always the same because singlets anddoublets cannot be distinguished.
Therefore, particles must be counted; simply measuring "concentration"will not work. In order to take into account the decrease in number density ofSPM particles (over short time frames), an approximation can be used for thetotal number of SPM particles. Start with the total number of particles at anytime:
(2-25)
and since a short timeframe is of interest, use a Taylor series approximationwhich yields
2-32
n.r 0- 1 - k n to s 1
nl
(2-26)
Therefore, in the rate expression for oil, the SPM concentration should bewritten as (to a "better" approximation)
cp
CO (1 - k t)P s(2-27)
where CO is the time = 0 SPM concentration in mg/l. The rate constant k canp s
be measured by counting particles. Thus, the SPM number density, not concen-tration, decreases linearly in time for small times. A nephelometer could beused to observe the tim~frame where the SPM particle density is linear.
particleare based
This example shows what the starting equations are for the particle-kinetics and the assumptions required. It is true that the kinetics
tration. "on "number density," yet the primary observable is usually "concen-There must be a relationship available which relates number density
to concentration in order for open-ocean "circulation" calculations to be made.Actual observations of open-ocean SPM kinetics should be made and interpreted(i.e., fast or slow relative to oil-SPM kinetics) before a general model is de-rived. It is possible now to "write" the equations for all interactions; how-ever, using these equations in a practical application is most likely impossi-ble.
The above example also illustrates the observations that must be madeand experimental variables controlled in order to obtain useable results. Itis currently not possible to obtain more than one or two derived quantities(i.e., rate constants) from a particle-particle kinetic experiment. These ex-periments must be "controlled" so that only one event is occurring (or two atmost) .
2-33
2.3.2 Kinetic Algorithm Use in an Ocean Circulation Model
Now consider how the kinetic algorithm will be used in an ocean-circulation model. The ocean-circulation model will be capable of transportingmaterial according to the mass balance equation. The kinetic algorithm will bewritten in a subroutine named SPMRTE (for SPM rate). The calling statementwill appear as
CALL SPMRTE (SPMC,SPMR,EV,TSTEP,NT)
where SPMC is an array which contains the SPM concentrations for all fractionsor types being considered, SPMR is an array which contains the SPM rates forall fractions or types (including oil drops) , EV is f./v, TSTEP is the (size of)the time step and NT is the number of SPM types being considered.
Physical parameters required are the constants which relate numberdensity to concentration for each NT type of SPM. This parameter will be namedZETA, be a dimensioned array, and be used as
NDEN(I)=ZETA(I)*SPMC(I) (2-28)
with NDEN declared as REAL*4 (as required). The kinetic rate constants for thecollision and sticking of component i with component j will be stored in an ar-ray KC(I,J) also declared REAL*4. These parameters must be entered before theprogram begins execution (i.e., similar to the way True Boiling Point distilla-tions are entered in the oil-weathering codes). Both ZETA(I) and KC(I,J) wouldbe passed to subroutine SPMRTE through a common block.
The calculation would proceed through a DO-LOOP to calculate the rela-tive decrease in number density of particles through a Taylor series approxima-tion
ZETA (I)=ZETA(I)*(l.-KC(I,I)*TSTEP) (2-29)
2-34
Then the rate expressions are calculated according to
SPMR(I)=KC(I,J)*SPMC(I)*ZETA(I)*SPMC(J)*ZETA(J) (2-30)
These rate arrays will be returned to the main program and then integrated.The main program also calculates how much SPM has entered (or left) the watercolumn through the bottom boundary and likewise for oil drops at the surface.The main program also must keep track of the sediment accumulated on the bottom(i.e., a material balance of sediment on the bottom in order to keep from flux-ing up something that is not there). Also, note that the boundary conditionsfor both sediment and oil drops are "fluxes", and algorithms for these fluxes(i.e, Grant's and Mackay's, respectively) must be encoded elsewhere.
Clearly, in programming these equations into a code, numerous "traps"will have to be included to prevent "nonsense" numbers from being generated.These traps will become apparent as real numbers are developed and calculationstried. The actual mathematics are relatively straightforward, the actual com-putation procedure (i.e., the integration, choosing step sizes, etc.) will be achallenge.
2.4 RESULTS OF OIL/SPM INTERACTION KINETICS DETERMINATIONS USING A 28LITER STIRRED CHAMBER
2.4.1 Background, Required Assumptions and Limitations of Experiments
As described in the Sections 2.1 and 2.2, the experimental procedurefor determining the oil-droplet and suspended-particulate interaction is basedon the continuity equation in which the rate term is identified. This rateterm for the interaction kinetics is first order with respect to oil-dropletconcentration and first order with respect to suspended-particle concentration.The rate expression is proportional to the energy dissipation rate to the one-half power.
In the beginning of this program, the rate-determining experimentswere conducted in the 28-liter stirred vessel illustrated in Figure 2-11
2-35
through 2-14. While initial experiments met with some difficulties,separatory-funne1 and filtration procedures were ultimately developed to allowdescrete measurements of mg/liter concentrations of dispersed oil, free SPM andoil/SPM agglomerates as a function of time (see Section 3.1 and Year One Inter-im Report for complete experimental details). In these experiments, the oil
1(fresh Prudhoe Bay crude, 2-day weathered and l2-day weathered) ...1was introduced as a surface slick, and turbulence was provided by a'propellerin much the same manner as described in Section 2.2.
One drawback to the experimental device was that its complexity andsize prevented an accurate measurement of the energy dissipation rate, f, suchthat the turbulent shear rate which is expressed as (f/v)1/2 could not beexperimentally determined to properly scale the kinetics expression. In orderto calculate the energy dissipation rate for an experiment, the power input canbe calculated from
P =wT (2-31)
suredw is the angulartorque (dyne-em)(dyne-em/sec).
velocity of the stirrer (radians/sec) and T is the mea-which yields the power delivered to the contents of the
Because all of the power delivered to the stirrer is
where
vesseldissipated in the entire fluid mass of the vessel, the rate of energy dissipa-tion per unit mass of fluid is
f =PVp
(2-32)
lWeathered Prudhoe Bay Crude oil was prepared by a 16 liter experimental spillin the flow-through outdoor wave-tanks at NOAA's Kasitsna Bay facility asdescribed in Payne et al. (1984). Chemical and Physical Properties of thefresh and weathered oil are presented in Table 2-10.
2-36
T11 IN.
1-
ILiCTRIC MOTOIt
OIUWATIRINTIR'ACI
I-J".I¥ IN","
NlATiNCI/COOUNCI COIU
AIR VlLOCITV ON MOVAaLIROO MOUNTID J CII UOViAIRIOIUWATIR INTI ••••ACI
I
?CHARCOAL 'IL TIREDAIR CONDITIONED AIR INPUT3 CM ABOVE A,R/OILIWATIRINTERFACE
TlNAX TRAPS" TTACHID TO'LOW ",O'ORTIONID 'UWS(Net ••••••••
OIUWATI •• 3C11i. •••••INTI ••••ACI t
•..--y IAWUNG 110'"'
ILiCTRIC MOTOR
ClNTUL TUU - •••• --.
c
MIXING SHA", -~..c:>--"--O
Figure 2-11. Prototype tank design for evaporation/dissolution and oil/SPMinteraction experiments.
2-37
2-38
Figure 2-12. Twenty-eight liter oil/SPM interaction chamber equipped withdirectional air manifold and stirring motor for introduction ofturbulence. Subsurface water samples are collected through thestockcocks inserted through the side of the glass chamber.
III ~
Figure 2-13. Dispersed oil droplets and SPM in the 28 liter stirred reactionchamber using l2-day weathered Prudhoe Bay crude oil and 53 pmsieved Jakolof Bay SPM.
2-39
Figure 2-14.
1Jf"'-",.
• ~., - , : • ,1 'i -~
"" ',,' ,','~,<
••
f
=..~I~
~
Twenty-eight liter oil-SPM interactionresidual dispersed oil droplets and SPMtermination of stirring turbulence.
chamber containingtwo minutes after
2-40
Table 2-10. Chemical and Physical Characteristics of Oil from Wave Tank t4 Oil/SPM Interaction Experiment
TimeHydrocarbon Concentration (019/9 oil)
Total Resolved Unresolved CompoundsInterfacial Tension (dynes/em)
Oil/Water Oil/AirViscosity iil38°C
(centipoise)Water Content(X by weight)
==================================================================================================================================Starting Crude 119 229 24.6 31.8 30 .30
48 hours 63.8 145 11.1 33.0 43 .11
12 days 21.5 104 11.5 34.6 800 6.3
where V is the actual volume of fluid in the vessel and p is the fluid density.Therefore, the working equation is
G (~)1/2v
(~)1/2Vpv
(2-33)
Attempts to install an "in-line" torque meter in the stirred chamber were un-successful due to serious propeller shaft allignment problems and the actualsize of the apparatus. Thus, the decision was ultimately made to discontinueuse of the 28-liter chamber and proceed with the smaller apparatus described inSection 2.2 where the energy dissipation rate could be successfully measured.It is significant, however, that with both systems, the turbulence in the ex-perimental solutions (i.e., derived from the propeller rotation and any resi-dent baffles) was just sufficient to maintain a nominal 50 mg/l suspended loadof sieved «53 ~m) particulate material from Jakolof Bay. Thus, although theapplied power and contained volumes were different, it is possible (to a firstapproximation) to assume similar turbulence levels necessary to just maintain
tionSPM loads in both the 4-liter and 28-liter systems. As described in Sec-2.2, the measured turbulent shear rate (E/v)1/2 for the smaller system was
-1sec Therefore, in order to proceed with the data analyses from experi-
the
160ments completed in the 28-liter system, a similar value will be assumed here.
The rate of a bimolecular reaction can be measured by following therate of disappearance of one or both of the reactants or by the rate of forma-tion of the product. From equation 2-3 in Section 2.1 the rate, R, of oil/SPMinteractions was given by
R = d Proddt
1.3 (E/v)1/2 k C Ca 0 p
(2-34)
Prod
rate of interaction (reactant disappearance or product formation,~g-oilSPM/liter'hr or mg-oilSPM/liter'hr with proper conversions)
measured oil-SPM agglomerate concentration (~g-oilSPM/liter)
where R
2-42
d" ." " (2/ 3)energy ~ss~pat~on per un~t mass cm sec
1/ ki ." " (2/ )~nemat~c v~scos~ty cm sec.
C o concentration of oil droplets (mg/liter)
CP
concentration of SPM (mg/liter)
For this derivation it should be noted that the designation ~g-oilsPM (or mg-oilSPM) represents the total mass of oil in ~g (or mg) associated exclusivelywith the SPM phase as measured by filtration and solvent extraction of the iso-lated "oiled" SPM sample and FID-GC analysis of the extract. For these calcu-lations the sum of all resolved peaks in the GC profile was used to quantifythe total hydrocarbon load on the SPM (see Section 3.1 for experimental de-tails). Thus, the term ~g-oilSPM/liter represents the concentration of oil as-sociated with all the SPM measured in a specific volume of sample.
Since R~g-oilsPM
l'hr(2-35)
ka
1 (2-36)mg (oil) . mg(SPM) mg
which is dimensionally similar to what was derived for k in Section 2.1 (i.e.,aunits of reciprocal concentration).
During the execution of any oil/SPM interaction experiment within the28-liter stirred chamber, free SPM loads were observed to decrease in an expo-nential fashion with time due to interactions with dispersed oil droplets (notsedimentation). At the same time, total free oil droplet concentrations wereobserved to increase due to changes in the oil/water interfacial surface ten-sion resulting from oil oxidation, water incorporation (into oil) and SPM coat-ing on oil droplets (presumably affecting both interfacial surface tension andsurface charge). Oiled SPM agglomerates increased in a non-linear fashionwhich approached some limiting value controlled by the initial SPM loading in
2-43
the experimental apparatus. These trends are shown graphically in Figure 2-15where equations 2-37, 2-38 and 2-39 are defined to describe the time seriesconcentrations of free oil droplets and SPM.
2.4.2 Results and Discussion of Experiments with Fresh, 2-Day Weathered, andl2-Day Weathered Prudhoe Bay Crude Oil and Jakolof Bay "SPM"
Actual free oil droplet concentration data for stirred chamber experi-ments with fresh, 2-day weathered and l2-day weathered Prudhoe Bay crude oilare presented in Figure 2-16. Plots of actual In C ICo vs time data for the
p pthree experiments are presented in Figure 2-17. From these plots it is possi-ble to obtain values for the slope, m, in equation 2-37 and k in equations 2-38and 2-39 which can later be used to explicitly solve for k the oil-SPM rateaconstant in equation 2-34. Values for m and k (along with correlation coeffi-cients) for the three experiments completed in the 28 liter stirred chamber arepresented in Table 2-11.
2.4.2.1 Oil/SPM Interaction Rate Constant with Fresh Prudhoe Bay Crude Oil
Rewriting equation 2-34 becomes
dProddt (2-40)
where Q
Substituting from equations 2-37 and 2-38 yields
dProddt
o -ktQ m t C ep (2-41)
Re-arranging the equation and taking the integral yields
2-44
10
mg= l·hr
2.5 C (mg/l)p
7.5C (mg/l) 5o
ttC CO + mt
C = CO -kt when 0
=e Cp equals the initial
0 0
P Pat t = O· CO = 0
SPM load charged into the water column (2-38)• 0
OJ:' CN C = m- t (2-37)
P -ktI
0
In - =(2-3Y)
.p-
COI.J1 where t is in hours
p
OiledSPM (mg/l)
t
Figure 2-15 Idealized time-series profiles of free oil (C ). free SPM (~) andoiled SPM loads in 28 liter stirred chamber e~periments.
70fresh6- 0
"- 60+ (0.16)x; ,2 = 0.972 y -0.28o
3o 50 2-day weathered<lJ(/I
"- ---B---.~ 40
Y -2.16 + (2.46)x; r2 = 0.98<, ....0U ..........I ....6.,-
12-day weathereden .30 6 /.<lJ ,0 8."-~ . ,
2.96 (3.20)x; r2 = 0.96.2 20 c: Q' y +C'1 6.E ,
10r
D0
0 10 20 .30 40 50 60 70 80time (hours from start)
Figure 2-16. Dispersed oil concentrations (mg total resolved hydrocarbons/liter of seawater) over time (hours after the spill event) forexperiments with fresh, 2-day weathered and 12-day weatheredPrudhoe Ba¥ crude oil. -Linear regression lines fitted to thedata and r values for each set of data are included in thefigure.
2-46
Ln(SPM-t/SPM-O) vs. Timefor Different Starting Oil Types
1.0
0.5
0.0.....•.•aI
-0.5:2a.U1;;-
-1.0I
:2a.-1.5U1
.E=
-2.0
-2.5
fresh oil
o---*------ 2 day weathered oil
----8 ---
12 day weathered oil6.
~ no oil-Jfo--
o
a 20 40 60 80 100 120 140 160 180200220
hours from start
Figure 2-17. Natural logarithms of the ratios of SPM concentrations at time _"t" hours to that at time - 0 hours versus time in experimentswith fresh, 2-day weathered and l2-day weathered Prudhoe Baycrude oil and no oil 2addition. The linear regression linesfitted to the data have r >0.89 for all plots.
2-47
Table 2-11. Values for m and k (equations 2-37 through 2-39) calculated fromdata plots in Figures 2-16 and 2-17.
Oil Typek
(hr-1)r m
(mg/!.hr)r
Fresh 0.0041 0.94 0.156 0.942-day weathered 0.0039 0.85 2.5 0.97l2-day weathered 0.0024 0.96 3.2 0.91
Note: r - correlation coefficient for linear regression lines fited to data inFigures 2-16 and 2-17.
2-48
f: 0 t -ktjdProd = QmC~te dt (2-42)
Prod-j t
QmCo [e (-kt-1) + const]p _k2 (2-43)
QmCo [const -p
-kte (kt+1)]k2 (2-44)
(kt+1) ][const -k2e+kt (2-45)
At time=O, no product has been generated. Thus for Prod=O, the
const
As t -> 00, equation 2-45 reduces a constant (i.e., the initial loading)
Prod Q m COp
From inspection of equation 2-45 it is apparent that a value for Q canbe determined by plotting measured Product concentration (~g oi1SPM/1iter) vstime and assigning values for Q until a reasonable fit to the data is obtained.Figure 2-18 presents such a series of computer generated curves for the freshPrudhoe Bay crude oil plus Jako1of Sediment SPM experiment. From the figure arange of values for Q of 0.05 to 0.08 is obtained. Using the value of 160
-1 for (€/1I) 1/2 and solving equation 2-40 yieldssec
-8 -7k = 6.7 x 10 to 1.3 x 10 l/mga
2-49
k==4.1e-3 Fresh Oil Expt Oil DataQ ran 9e from O.OJ toO. 12
PROD1000900800700600500400JOO200100
a0 10 20
.............
..•..•••./ ••.•..•/ »:"
SYM
JO 40 50 60TIME
............... q 1
............... q5
.......... - .... q9............... q3.. ..... q 7
70 80 90 100 110
<:> <:> <:> labq4q8
--q2q6ql0
F~gure 2-18. Computer generated plots of product concentrations (~g oil SPM/liter seawater) versus time (hours after spill event) for valuesof Q ranging from 0.03 to 0.12. Experimental data points areindicated by circles for experiment with fresh Prudhoe Bay crudeoil and Jakolof Bay sediment (~ 53 ~m).
2-50
These values agree very well (within a factor of three) with the valueof 1.8 x 10-7 l/mg obtained with the smaller reaction vessel described in Sec-tion 2.2. Thus, in two completely different experimental systems, using dif-ferent parameters to measure the rate of reaction (free oil droplets measuredby microscope versus oil-SPM agglomerates measured by selective isolation, sol-vent extraction and gas chromatography), very similar reaction rate constantswere obtained. This very close agreement is particularly significant becauseit validates the overall approach of the two independent methods and adds cred-ibility to the values obtained for the rate constant of the interaction offresh Prudhoe Bay crude oil and <53 ~m Jakolof Bay SPM.
2.4.2.2 Oil/SPM Interaction Rate Constant with 2- and l2-Day Weathered CrudeOil
This same approach with the data sets obtained from the 28-literstirred chamber experiments with Jakolof Bay SPM plus 2 and l2-day weatheredPrudhoe Bay crude oil yielded:
ka
-83.3 x 10 l/mg for 2-day weathered oil
2.9 x 10-8 l/mg for l2-day weathered oilka
These rate constants are in the same order of magnitude, but slightlylower than the rate constant obtained in the 28 liter experimental system using
.fresh Prudhoe Bay crude oil. Inspection of Figures 2-17 and 3-6(a), which showI
a more rapid decline of SPM with 2-day and l2-day weathered oil, would lead tothe expectation that the more rapid decline of SPM with these weathered oilsshould yield a higher rate constant, k. In actual fact, with the 2- and 12-
aday weathered oil, the oil droplet concentrations in the water column were anorder of magnitude higher than the oil droplet concentrations with fresh Prud-hoe Bay crude oil. This reflects the lower oil/water interfacial surface ten-sion in the weathered crude (Table 2-10) and, hence, the tendency for the oilto disperse into the water at higher oil droplet concentrations under a con-stant energy turbulent regime.
With dispersed oil concentrations being so much higher in the experi-ments with the 2- and l2-day weathered oil (see Figure 3-6(b), any SPM which
2-51
interacted with the dispersed oil phase tended to remain in the dispersed orsurface oil phase rather than remain in the SPM phase of whole water samplesthat were collected during experiments. Therefore, when time-series aliquotswere removed from the stirred chamber and allowed to stand in the separatoryfunnel, the oil-SPM aggregates remained in the "floating" or dispersed oilphase and were significantly under-represented. As a result, when the forma-tion of product in milligrams of oil associated with SPM per liter is plottedversus time, the overall maximum concentration of product is significantlyunder-represented. This results in smaller values for the lumped-parameterconstant, Q, necessary to obtain an idealized fit to experimental data. As aresult of Q being artifically small, solutions of equation 2-40 will yield val-ues of k (at a constant energy dissipation rate) which are also low.a
These results clearly show the efficacy of the smaller oil-SPM inter-action system described in Section 2.2. Specifically, with the 4-1 system theoil droplet number density and concentration can be controlled, such that oilconcentrations will not be too much in excess of the SPM phase.
2-52
3.0 CHEMICAL PARTITIONING AND PHYSICAL BEHAVIOR OF DISPERSED OIL DROPLETSAND OIL/SPM AGGLOMERATES
3.1 SEPARATION AND ANALYSIS OF SPM AND DISPERSED OIL FRACTIONS BY INHERENTDENSITY DIFFERENCES
To obtain better estimates of the discrete hydrocarbon quantities inthe SPM and dispersed oil fractions, a sub-surface whole water sample was col-lected from the experimental chambers (at pre-determined time intervals) andplaced in a glass separatory funnel that was completely filled with solution.The sample in the separatory funnel was maintained in a stationary position fora sufficient period of time (2 hrs) to allow for inherent density differencesbetween dispersed oil droplets and SPM to produce a physical separation betweenthe two fractions (i.e., oil droplets rise and SPM sinks in the separatory fun-nel). Losses of specific hydrocarbons due to volatilization of lighter frac-tions into an overlying head space are minimized because the separatory funnelis completely filled with sample. This sampling protocol subsequently allowsfor three reasonably discrete "phases" to be collected from the separatory fun-nel: 1) an "SPM phase" that is comprised of oiled and un-oiled SPM accumulatingat the bottom of the separatory funnel, 2) a "dissolved phase" that is com-prised of the water in the separatory funnel (excluding the upper oil layer)and 3) a "dispersed oil phase" that is comprised of the oil layer at the top ofthe separatory funnel. The "SPM" and "dissolved phases" are physically separ-ated and extracted with methylene chloride to recover hydrocarbons. The "dis-persed oil phase" is recovered with solvent rinses following removal of the"SPM" and "dissolved phases" from the separatory funnel.
Although this separatory funnel approach yields three discrete sam-ples, a limitation in the general application of this procedure became apparentduring initial experiments with oi1-SPM-seawater systems. For distinctions be-tween hydrocarbon quantities contained .in the "dissolved" and "SPM phases" tobe accurate, all of the SPM in a water sample must collect at the bottom of theseparatory funnel. Observations during experiments indicated that a portion ofthe SPM often adhered to the sides of the funnel rather than sinking to thebottom. Furthermore, this trend was more pronounced when SPM particles becamemore "oiled". This resulted in the following limitations: 1) an underestima-tion of the total amount of hydrocarbons contained in the "SPM phase" of asample (due to not only incomplete recovery of all of the SPM in the water
3-1
phase but also the possible loss of more heavily "oiled" particles that prefer-entially adhere to the funnel walls) and 2) an overestimation of hydrocarbonquantities in the "dissolved phase" due to'inc1usion of SPM adhering to theseparatory funnel walls. The latter "dissolved phase" could be further mis-leading since it would likely contain the relatively insoluble aliphatic com-pounds (specifically associated with the SPM) that would not in reality existin the "dissolved" phase of the sample. Hence, a means needed to be developedto insure that SPM particles were not included in the "dissolved phase" of asample.
To achieve the desired separation between "dissolved" and "SPM"phases, the following general approach was adopted. After "differential phasesettling" in the separatory funnel, the aqueous portion of a sample (i.e., con-taining both SPM and water) was vacuum filtered through a 47 rom diameter, 0.4~m pore size polyester membrane filter (Nuclepore catalog number 181107). Theresulting water filtrate (free of SPM) was then extracted with methylenechloride and analyzed for the "dissolved fraction" of hydrocarbons, and theparticulate matter retained on the filter was extracted as described below toquantify the "SPM fraction" of hydrocarbons.
3.1.1 Method Validation for Polyester Filter-Vacuum Filtration Procedure
Filter blanks were processed through the entire vacuum filtrationprocedure to insure that: 1) the filter was resistant to the extractionsolvents (i.e., methanol and methylene chloride) and did not contribute anyinterferring peaks during subsequent FID-GC analysis; 2) the filter wouldmaintain its structural integrity through all manipulation steps of thefiltration process plus pre- and post-filtration measurements of filterweights for determination of the exact mass of SPM filtered and extracted; and3) the filter would not require pre- wetting with an organic solvent (e.g.,methanol) to facilitate passage of aqueous solutions.
To evaluate whether the solvent rinses (i.e., methanol and methylenechloride) of the filters were sufficient to recover all of the oil from theSPM, a spike/recovery validation experiment was performed. The spiked materialwas prepared by mixing 40.8 mg (dry weight) of the < 53 ~m sieved Jakolof sedi-
3-2
ments with 600 m1s of seawater and 8.0 m1s of fresh Prudhoe Bay crude oil in a1000 ml glass beaker for 9 hours. This mixture was transferred to a separatoryfunnel, and differential phase separation was allowed to occur as describedabove. The water and SPM phase was then vacuum filtered (30 cm Hg) through apolyester filter, and the water filtrate was analyzed as the "dissolved phase"for hydrocarbons. The filter was then vacuum extracted with 10 m1s ofhydrocarbon-free distilled water (to remove residual seawater and salt)followed by 15 m1s of methanol (to "dry" the sample) and 30 m1s of methylenechloride. The combined methanol-methylene chloride filtrates were partitionedagainst seawater, and the resulting methylene chloride fraction was transferredto a collection flask. The remaining seawater-methanol solution was back ex-tracted with methylene chloride, and the combined methylene chloride extractswere condensed and analyzed by capillary column FlO-GC. To insure that com-plete extraction of the SPM had occurred, the polyester filter containing theextracted SPM was re-extracted a second time (using the vacuum technique) withan additional 30 mls of methylene chloride that was concentrated and analyzedseparately.
The FlO gas chromatogram of the Prudhoe Bay crude oil used in thistechnique validation experiment is presented in Figure 3-la, and the chromato-gram of the seawater filtrate (dissolved phase) is presented in 3-lb. Compari-son of the two chromatograms demonstrates that the aliphatic n-alkanes so ap-parent in the parent crude oil do not appear in the "dissolved phase" of thesample. The peaks that are present in the "dissolved phase" correspond only toaromatic hydrocarbons, which are characterized by greater water solubilities(Payne et a1., 1984). The FlO chromatograms of the first solvent rinse of theSPM polyester filter (1.e ., the normal" SPM" phase) and the second solventrinse of the filter are presented in Figures 3-1c and 3-ld, respectively. Thenormal "SPM phase" (Figure 3-lc) has a chromatographic profile for n-a1kanesand other aliphatic and aromatic compounds that is very similar to that of theparent crude oil (Figure 3-1a), except that the more volatile lower molecularweight components are partially missing. The latter observation reflects the
3-3
-~~~- -----~- - - -
r I. ~~ . ,- " • " . r' "., r " r • " • r ..(a)
.:. .. r r_ " I r ~ '" .•0- " I. r r' ..,r_
D r .-•• r ..., ~ ••.,D
:; •,..0 .•.. .. •.. D.- .• ".. .. I:• ••.- II..• ,-
,; ...• .- e.• r, .•r· ....• ..
"
J ::..:s :; fee '.... : _r
• r _'01 " r.;e .. II . ._~, . t :: 0'.,,-,v,)
I.r:--
(b)
F1~ 3-1a Uleathend Pn.dme ~ crode 011 used for experillBtal oIl-SA41eter ~tan. 19.2101 ol1/llm ulmetl1Ylenechloride; 1 ul irUected.
Fi~re 3-1b llDissolvej JIlase" fran experillB1tal oil-SRot-water ~tan. 600 mls sea water, 400 ul post-i rliect 10n volune, 1 u1 1l\iected.
(e)
w (d)I
V1
...,.• .. •• • . •.. .. .. ,;
t'.. ...." . ,..• .. ..
•• • .. •;; " . ,. O'. •~ • .. ••• .. .... O'O'
I
j••,a;;
t-J ii,;,•
F1~ 3-1c 1tS1f4,naselt fran experinBtal oj l-Sl"-water ~t8n.volllE, 1 ul 1r\iect8t.
Fi~re 3-1d Secordmetttylenechloride Mnse of fi lter fran "S1f4p.aseH in Fi~re 5c. 400 ul post-injectionvolllE, 1 ul inject8t.
40.8 au cry SIf4, 400 ul post-inject~on
selective evaporation (and dissolution) of these compounds during the initial 9hour stirring 'phase of the experiment when the oil-SPM-seawater system was opento the atmosphere. Because the second methylene chloride rinse of the filter(Figure 3-1d) yielded a chromatogram with essentially none of the oil indicatedin Figure 3-lc, the solvent rinse sequence in the filter processing protocol(i.e., 15 mls methanol followed by 30 mls methylene chloride) appears to benearly 100% efficient in recovering petroleUm hydrocarbons that were adsorbedonto the surfaces of the SPM.
It should be emphasized that this polyester filter-vacuum filtrationprocedure is designed to recover hydrocarbons that are rather loosely adsorbed(1. e., "wetted") onto the surfaces of SPM particles (e.g . , adsorbed oildroplets, oil films and "dissolved" compounds that have partitioned onto theSPM). The purpose of the procedure is not necessarily to extract compoundsthat may be more intimately associated with the internal matrices of SPMparticles. However, to evaluate extraction efficiencies from "natural" sedimentsamples, a reference sediment containing known amounts of a variety of aromaticcompounds was extracted with the polyester filter-vacuum filtration procedure.Duwamish III reference sediment supplied in the NOAA-sponsored Status andTrends Program (Dr. W. MacLeod, NOAA, Seattle) was used as a test material. Toestimate procedural variability, three subsamples of this sediment (eachconsisting of approximately 1 gram dry weight) were extracted with thepolyester filter-vacuum filtration procedure and analyzed by FID-GC. Threeinternal standards (dB-naphthalene, dlO-acenaphthene and d12-perylene) wereadded to each sediment subsample immediately before extraction to estimate andcorrect for internal standard recoveries in the procedure. Final compoundestimates from these samples were compared with values reported by the NOAAparent ·lab (W. MacLeod) that used the much more rigorous Status and Trendssediment extraction procedure. The latter procedure involves extraction ofsediment with solvents for approximately two days, whereas the sediment withthe polyester filter-vacuum filtration procedure is exposed to the extractionsolvents for only approximately 60 seconds. The results of the extractiontests are summarized in Table 3-1. Keeping in mind that the polyester filterprocedure involves a much less rigorous extraction sequence, the results in thetable indicate that the vacuum filtration sequence is remarkably efficient for
3-6
Table a-t. Aromatic Hydrocarbon Concentrations---Ouwamish III SedimentPolyester Filter Technique vs. NOAA Status & Trends Procedure
PE filter procedure NOAA S&T procedure I % PE filter IICompound Mean CV Mean CV I of NOAA S&T I I
(ng/g) (%) n (ng/g) (%) n I cone. ""naphthalene NO 3 340 35 28 0 II2-methylnaphthalene 82 37 3 160 19 28 51 IIl-methylnaphthalene 110 28 3 110 25 28 100 II---------- - - - IIbiphenyl NO 3 36 29 28 o II2,6-dimethylnaphthalene 81 47 3 72 21 28 113 IIacenaphthene 233 31 3 330 13 28 71 Ifluorene 242 31 3 330 17 28 73 Iphenanthrene 1868 19 3 2300 10 28 81anthracene 483 14 3 620 56 28 781-methy1phenanthrene 255 13 3 210 13 28 121fluoranthene 3201 20 3 3600 13 28 89pyrene 3520 21 3 3900 11 28 90------ - - - - - - - -,,- - - - -benz (a)anthracene I 1069 21 3 II 1700 12 28 63chrysene I 1273 25 3 II 3000 15 28 42benzo(e)pyrene I 1075 10 3 I 1800 11 28 60benzo(a)pyrene " 1603 19 3 I 2000 10 28 80perylene II NO 3 I 600 15 28 0dibenz[a,h]anthracene II NO 3 I 330 22 28 0
" III III I
" I-Std Recovery (%) I I-Std Recovery (%)Internal Standard 10 " Mean CV n I Mean CV n
II Id8-naphthalene " 39 15 3 I 79 11 28dlO-acenaphthene " 60 8 3 I 90 7 28d12-perylene II 114 13 3 I 74 16 28
... -_ ......... -_ .............................................
NO = not detected
3-7
recovering the specified hydrocarbons from the reference sediment samples.
3.2 UTILIZATION OF THE OIL SEPARATION TECHNIQUE IN OIL-SPM INTERACTION ANDSEDIMENTATION RATE STUDIES
As discussed in Sections 2.2 and 2.4, similar oil-SPM interaction rateconstants were obtained from the experiments conducted in the 4 and 28 literreaction chambers. One of the benefits of the larger (28 liter) experimentalchamber was the generation of significant quantities of oiled SPM to allow fordetailed chemical characterization of oil after interaction with suspendedparticulate material and/or sedimentation.
To obtain information about the oil content and composition of varioussample types (e.g., SPM, dispersed oil or dissolved phases), several analyticaldetection methods can be considered for quantitation of hydrocarbons. Thesemethods include infrared (IR) and/or ultraviolet (UV) spectroscopy or flameionization detector gas chromatography (FID-GC). It is worthy of note,however, that with any of these techniques, extensive wet chemistrymanipulations (i.e., sample workup including gravimetric analysis, waterremoval, solvent extraction and solvent concentration) are required before anyinstrumental analysis (IR, UV or FID-GC) can be initiated.
Both IR and UV detection have major limitations that severely minimizetheir usefullness for the ultimate purpose of current oil-SPM modeldevelopment. For example, IR requires initial sample extraction with ultrapurefreon (CC12F2) or carbon tetrachloride (CC14) or exchange of all hydrocarbonsin the final sample extract into a solvent such as freon. This is requiredbecause IR uses the C-H stretch to quantify hydrocarbons such that Ci-H bonds intypical final extract solvents (e.g., methylene chloride, hexane, toluene)would preclude petroleum hydrocarbon analysis. Direct extraction of wet SPMsamples with freon or carbon tetrachloride (without prior methanol drying)yields unacceptably poor hydrocarbon recoveries. UV suffers from the followinglimitations: 1) it requires that the final sample extract be in ultrapure
impurity contamination; and 2) it is affected by compound specificspectrograde solvent (e.g., cyclohexane) to minimize background solvent
oil-weathering losses (i.e., evaporation and/or aqueous dissolution during
3-8
experiments) of particularly sensitive aromatic ring compounds from oil oroi1ed-SPM. The latter weathering losses present a particular challenge forselecting appropriate standard oil mixtures to quantify experimental sample oilextracts by UV. Both IR and UV also suffer from interferences due toextraction of any natural background (e.g., biogenic) hydrocarbons in finalsample extracts. However, perhaps the most severe shortcoming of both IR andUV for the stated purpose of this program regards their inabilities to provideinformation on true boiling point (TBP) cuts in oil samples. Neither IR nor UVprovide any information about TBP content in samples.
In contrast to the preceding limitations, FID-GC can provide much ofthe required information needed to quantify the content and composition of oilin samples. Attractive properties of FID-GC include the following: 1) it iscompatible with a variety of final sample extract solvents (e.g., methylenechloride, hexane, toluene); 2) it allows for potential distinction betweenanalytical contaminants and valid sample hydrocarbons if ~he two occur atdifferent chromatographic retention times; 3) it allows for evaluation and anynecessary corrections to be made for compound specific weathering losses fromoil during the course of experiments; 4) it allows for evaluation and possiblecorrection for natural background (e.g., biogenic) hydrocarbons in samples; and5) it allows for direct estimation of TBP cut content in a given sample. Thelatter information is derived from either an existing knowledge of FID-GCelution profiles for specific TBP cuts in oil (e.g., Payne et al., 1984) orsimilarly derived information for different oil types. Therefore, TBP cut aswell as individual compound concentration information for sample extracts canbe obtained with FID-GC. Although the following discussion of experimentalFID-GC data only deals with information for specific compound or total summedcompound concentrations, modifications are currently being incorporated intothe SAIC FID-GC data reduction code to yield direct information about specificTBP cut concentrations in reduced sample extracts.
Using FID-GC procedures described in Payne et al., (1984) analyseswere performed on numerous samples from experiments with both the 4 and 28liter systems. Among other purposes, such measurements were utilized todetermine total oil loadings in both the dispersed oil droplet and SPM phasesof experiments to estimate kinetic rate constants for oil-SPM interactions. In
3-9
addition to these oil "loading" estimates, however, the combination of themembrane filter separation technique and the normal data reduction procedurefor FID chromatograms of oil samples (Payne et al., 1984) allowed for detailedanalyses of component-specific hydrocarbon compositions in a variety of sampletypes. Such samples included not only the previously described dispersed oildroplet, SPM and dissolved phases of whole water samples but also oil samplesbefore and after "blending" to generate small oil droplets for oil-SPM kineticrate studies (in the 4-liter system) and samples of "sedimented" SPM that werecollected from the bottoms of both stirred and settling chamber studies.
Although this component specific information is not absolutely essen-tial for kinetic or sedimentation rate estimates, it does have relevance forpotential biological implications that could derive from oil-SPM interactionsin aquatic environments. Specifically, the content of toxic compounds in oildroplets associated with SPM could affect aquatic biota in at least two ways:1) oiled SPM that remains suspended in the water column can impact pelagic andepibenthic organisms that utilize filter feeding as a means of obtaining foodand 2) oiled SPM that is incorporated into sediments (1.e., is "sedimented out"of the water column) can impact benthic fauna that either live in associationwith or ingest sedimentary material in their feeding process. Compounds ofparticular interest for such considerations include various aromatic hydrocar-bon components (e.g., mono- and dicyclic aromatics and naphtheno-aromatics)that have been shown to be particularly toxic to impacted aquatic biota (e.g.,Hyland and Schneider, 1976; Johnson, 1977; Patten, 1977). Because FID-GC anal-yses are routinely performed anyway to estimate "oil loadings" in various sam-ple phases for the kinetic and sedimentation rate experiments, it is reasonableto include discussions of compound specific detailed chromatographic analysesof oil samples. Beyond the immediate scope of this project to provide inputregarding oil-SPM kinetic rate estimates, such information should be of inter-est to MMS's long-term stated purpose of incorporating oil-SPM interaction rateestimates into "biological effects" models.
3-10
3.2.1. Oi1-SPM Sedimentation Rate Studies.
Experimental studies in the 4 liter system to determine kinetic rateconstants for oil droplet-suspended particulate matter (SPM) interactions havebeen previously discussed in section 2.2. In one of these kinetics experi-ments, an "add-on" study utilized the oil drop1et-SPM solution generated in theexperiment to evaluate the effects of oil drop1et-SPM interactions on sedimen-tation rates of the SPM. These results are discussed below.
Sedimentation rate experiments with oiled SPM were initiated by transfer-ring approximately 1 liter of an oil drop1et-SPM-seawater solution generated atthe end of an oi1-SPM kinetics rate experiment to each of three vertical set-tling chambers (i.e., 1 liter graduated glass cylinders). Blended fresh Prud-hoe Bay crude oil and 53 ~m sieved Jako10f Bay sediment were used for the kine-tics rate experiment. After allowing the solutions to remain undisturbed inthe graduated cylinders, samples of known volume were withdrawn from a speci-fied depth in the cylinders at time intervals of 0, 15, 35, 60, and 110 min-utes. The samples were vacuum filtered «30 cm Hg) onto pre-weighed, 0.4 ~mpore size polyester membrane filters. Subsequent treatment of the filter sam-ples for both SPM gravimetric analyses and FID-GC extraction and analyses aredescribed in section 3.1. above. For an experimental control, an identicalsedimentation experiment was performed with the same sieved Jako10f Bay sedi-ment that had not been exposed to a solution of blended oil droplets.
The results of the measured SPM concentrations over time in the set-tling chambers for the experiments with and without the blended oil dropletsare illustrated in Figure 3-2. Because three identical settling chambers wereused in each experiment, the data points represent mean values with one stan-dard deviation unit being indicated by vertical bars. As indicated in the fi-gure, prior "oiling" of the SPM (1.e., during the preceding kinetics rate ex-periment) did not seem to substantially affect the rate at which the SPM set-tled out of the water column at the oil to SPM loading (ratio) considered.This may not be the case at higher relative SPM concentrations or whenf10cu1ation leading to larger oi1/SPM agglomerates occurs. Additional work iscurrently being completed with different oi1/SPM ratios, SPM types (and sizes)
3-11
55 ~ tJ ",
f50
45 ~'-
40 t2< 35...;~e 30"0
en 25E0 20'-0>
E 151050
0 20
SPM Concentrations: Oiled vs. UnoiledSedimentation Experiment--4 Liter System
Plus Oilaj
Minus Oil
40 60Time (minutes)
80 100 120
:igure 3-2. Gravimetric concentrations of SPM in sedimentation experimentsconducted with oiled and unoiled Jakolof Bay sediments (sieved to~53 ~m). Oiled sediment was obtained from a parent oil-SPMkinetics rate experiment.
3-12
and oil types to investigate this sedimentation behavior further.
3.2.1.1. FID-GC Analyses of Oil Fractions in the Sedimentation Experiment
The compound specific composition of oil was investigated in a varietyof samples from the sedimentation rate experiment in section 3.2.1. Such sam-ples included the initial unblended and blended oil solutions used for the par-ent oil droplet-SPM kinetic rate experiment, oil associated with the SPM thataccumulated on the floor of the sedimentation chamber after 110 minutes of set-tling, and oil associated with the SPM that remained suspended in the watercolumn after 110 minutes of settling time. Individual compounds were consider-ed in terms of 1) their absolute concentrations (e.g., 10-6 grams of compoundper gram dry weight of SPM) and 2) the ratio of their concentrations to that ofthe n-alkane nC2l in the sample (i.e., compound/nC2l for both n-alkanes andaromatics). As discussed in the June 1986 quarterly progress report to MMS(SAlC, 1986), the use of concentration ratios can assist in detecting compoundspecific trends that might otherwise be obscured by either large absolute con-centration differences between sample types (e.g., whole oil and oil associatedwith SPM) and/or different concentration units (e.g., per gram dry weight ofsediment or per liter of seawater).
Prior to investigating compositional differences between oil containedin the various sample fractions in the sedimentation experiment, an evaluationwas made of the changes in composition due to the effect of the precedingblending effort (i.e., oil in seawater in a mechanical blender) that was usedto generate the dispersed oil droplets for the parent oil-SPM kinetics rateexperiment. Figure 3-3 presents concentration ratios for the various n-alkaneand aromatic compounds (relative to nC2l) in the initial pre-blend Prudhoe Baycrude oil and the blended seawater-oil solutions at 2 and 32 minute time pointsin the kinetic rate experiment. Substantial losses of both n-alkanes belownC17 and the measured aromatics appeared to occur as a result of the initialmechanical blending process, but additional losses were minimal thereafter(i.e., ratios at the 2 and 32 minute time points were very similar).
3-13
The "oiled" sedimentation rate experiment in section 3.2.1. used the
Ratios: nC(X)/nC21Oil Used for SPM Interaction and Sedimentation Experiments
4 Liter System
2.4
2.2
2.0
1.8
1.6
1.4
Pre-blend oile
Blended oil---2 min----&---
o·zo....
.: ~.Ii. ,
A'" ". ,III
r
Ai. ~'.r. .
0.6 :....:'
0.4 L ..../.s-,a0.2 tf,,/'
(!'0.0 ~.L-. __L-:,--I I I • , ! I , I ! I I
8 10 12 14 16 18 20 22 24 26
Blended oil---32 min.il.
1.2
1.0
0.8
28 30 32
n-alkane carbon number
Ratios: Aromatic Cmpd./nC21Oil Used for SPM" Interaction and Sedimentation Experiments
4 Liter System
0.6
0.5
0.4
0~ 0.3o....
0.2
0.1
0.0
~ Pre-blend oil
IIBlended oil---2 min
~ Blended oil---32 min
biphenyl 1.3-di~eNo 2.3.6-tri~eNo
Aromatic Compound
Figure 3-3. (a) Concentration ratios of n-alkanes to nC21 in oil samples fromthe parent oil-SPM kinetics rate experrment. The seawater-oil-SPM solution from the 32 minute time point was subse-quently used for the oiled SPM sedimentation experiment.Comparable concentration ratio information for selectedaromatic compounds (diMeNa - dimethylnaphthalene; triMeNa _trimethylnaphthalene).
3-14
(b)
seawater-oi1-SPM solution generated at the end (32 minute time point) of one ofthe 4-1iter reaction vessel experiments described in Section 2.2 (i.e., Table2-2). After the sedimentation solution had remained stationary for 110 minutesin the settling chambers, samples for FID~GC analyses were collected of 1) SPMon the bottom of the chamber (i.e., SPM that had settled out of the watercolumn during this time interval) and 2) residual suspended SPM in the watercolumn (i.e., SPM that had remained in suspension). Figure 3-4 illustratesabsolute concentrations of n-a1kanes and aromatic compounds in these two SPMfractions. As indicated, the sediment on the bottom of the settling chamberhad higher oil "loadings" of both n-a1kanes and aromatic compounds than thatremaining in suspension. Because the hydrocarbon concentrations for both the"sedimented" and "residual suspended" SPM samples are reported per gram dryweight of SPM, this indicates that higher oil loads were associated with SPMparticles that settled out of the water column. Furthermore, differencesbetween compound concentrations in the "sedimented" and "suspended" SPMfractions were greater for compounds with lower molecular weights. Ratios forthe n- alkane and aromatic compounds relative to nC2l are presented in Figure3-5. Information from this ratio eliminates any uncertainty in interpretingchemical fractionation trends that might be obscured by differences in absoluteconcentration values and illustrates that the chemical fractionation trendsevident in Figure 3-4 are still valid. Because oil droplets associated withboth the "sedimented" and "suspended" SPM fractions should be subject tocomparable tendencies for dissolution losses of compounds into the ambientwater, the enhanced retention of both the aromatic and lower molecular weightn- alkane compounds in the "sedimented" SPM may reflect the existence of largeroil droplets associated with the SPM fraction that "settled out" of the watercolumn (i.e., larger droplets will have smaller surface to volume ratios, whichwill favor slower rates of compound dissolution into the adjacent water phase).
Similar trends in the compound specific fractionation of oil associat-ed with "residual suspended" and "settled" SPM phases have been observed instirred chamber experiments with the larger 28 liter system (Section 3.2.2.3.below). Higher absolute concentrations of aliphatic and aromatic compoundshave been observed in SPM that has a tendency to sink out of the water column.Furthermore, examination of compound/nC21 ratios indicates that compounds with
3-15
Figure 3-4.
80
60 ~
4°lL~20
a'2._""e~o \ _""e~o 'o\pnef''j\_(f\""e~0'2_d\""e~o _tf\""e~o pnef'
\. v. '2,),0
Aromatic Compound
900
800~Q.. 700(f)-0 600.•...~e 500
"t:l
E 4000'-0'<, JOOE0'- 2000':J
100
a8
180
160
Sediment Concentrations: n-alkanesSedimentation Experiment--From 4 Liter System
Sedimented SPM
~Bi 140-o 120
a
Suspended SPM·······0···
a··[t.·a.
.d '0.
g .0 ....0....0... 0-...0
.0
D
10 12 14 16 18 20 22 24 26 28 JO J2n-alkane carbon number
100
SPM Concentrations: AromaticsSedimentati'on Experiment--From 4 Liter System
IISedimented SPM
~ Suspended SPM
(a)
(b)
Absolute concentrations"sedimented" and "residualminutes of settling in theComparable concentrationsmethylnaphthalene; diMeNatrimethylnaphthalene; phen
of n-alkanes associated withsuspended" SPM fractions after 110oiled sedimentation experiment.
for aromatic hydrocarbons (MeNa _dimethylnaphthalene; triMeNa -
phenanthrene) .3-16
Ratios: nC'(X)/nC21Sedimentation Experiment--From 4 Liter System
2.0
1.8
1.6
1.4
1.20:;; 1.00...
0.8
0.6
0.4
0.2
0.0
./,--Q"l!I-- ---·Q"lll\
···,..~···,····,.
",···,.,.,···,..1!I
initiol oil
••sedimented oil
----B----suspended oil
..... 4\ ....
8 10 12 14 16 18 20 22 24 26 28 30 32n-alkane carbon number
Ratios: Aromatic Cmpd./nC21Sedimentation Experiment--From 4 Liter System
o...•o•..
IISedimented SPM
~ Suspended SPM
Aromatic Compound
Figure 3-S. (a) Concentration ratio. of n-a1kan.. to nC21 in the initialblended oil (2 ainut.. after b1endins) and the final"sedimented" and "residual suspended" SPM after 110 minutesof settling in the oiled sedimentation experiment.
(b) Comparable concentration ratio information for .electedaromatic compounds (.e. Fiaure 3-4(b) for compound identifi-cation).
3-17
higher water solubilities (e.g., aromatics and lower molecular weightn-alkanes) have a greater relative enhancement in the oil fractions of the"sedimented" as opposed to "residual suspended" SPM. This higher absolute"loading" and selective enhancement of more toxic hydrocarbon compounds (e.g.,various di- and tricyclic aromatics) in "sedimenting" SPM phases can have im-portant biological implications for bottom fauna. This would be particularlytrue for organisms inhabiting areas where such "oiled" SPM might become concen-trated in the surface sediments.
3.2.2. SPM Load and Hydrocarbon Information from Oil-SPM Interaction Studieswith the 28 Liter Stirred Chamber System.
One advantage of the larger 28 liter test chamber presented in section2.4. (i.e., as opposed to the 4 liter chamber discussed in section 2.2.) is thetotal volume of experimental solution available to be sampled. The larger to-tal solution volume allows for not only larger sample volumes to be collectedat anyone time but also multiple samples to be collected over longer samplingtime periods. While experiments in the 28 liter chamber do suffer from certainexperimental limitations (section 2.4.1.), it has been determined that esti-mates of oi1-SPM interaction rate constants for fresh Prudhoe Bay crude oil and53 ~m sieved Jakolof Bay sediments can yield comparable values with both the 4and 28 liter systems (section 2.4.2.1.).
As discussed in section 2.4., three experiments were performed in the28 liter system with seawater, 53 micron sieved Jako10f Bay sediment and eitherfresh, 2-day weathered or 12-day weathered Prudhoe Bay crude oil. As a con-trol, a fourth experiment was conducted with the Jako10f sediment and seawater,but without any addition of oil to the system. Sample collection and process-ing protocols used in these experiments are discussed in section 3.1. Estima-tion of rate constants for oi1-SPM interactions from these experiments has al-ready been presented in section 2.4. A further discussion regarding SPM loadand hydrocarbon measurements during the course of these experiments is present-ed here.
3-18
3.2.2.1. Effect of Prior Weathering History of Prudhoe Bay Crude Oil on SPMLoads and Dispersion of Oil into the Water Column over Time.
Figure 3-6a illustrates SPM loads over time in the water column of thefour experiments in the 28 liter system. For the SPM type used and the turbu-lence level provided to the system, there appeared to be little or no tendencyfor the SPM load to decline in the absence of oil. In fact, the SPM load actu-ally increased with time (after 60-80 hours) due to processes that appeared tobe related to activities of microorganisms that were observed with lightmicroscopy in the system. Although microscope facilities were not availableduring the experiments with the three types of Prudhoe Bay crude oil, there wasno indication of microorganism-mediated processes affecting SPM loads in theseexperiments. The presence of toxic hydrocarbon compounds derived from the oil(e.g., dissolved aromatics) may have inhibited the growth of microorganisms inthe latter systems.
The levels of SPM declined over time in all three experiments with thecrude oil (Figure 3-6a). Because SPM was not observed to accumulate on thefloor or walls of the chamber during the experiments, the declining SPM loadswere indicative of incorporation of the SPM into the dispersed oil dropletsand/or the surface oil slick. In contrast to the system receiving fresh crudeoil, the rate of decline in the SPM load in the water column was much acceler-ated in the presence of both the 2-day and 12-day weathered oils. Because theabundance of polar compounds typically increases in weathered oils due to re-actions such as photochemical and microbial oxidation (e.g., Payne andPhillips, 1985; Karrick, 1977), the more rapid declines in SPM loads withweathered oil may have resulted from enhanced interactions between the SPM anda weathered oil phase that was characterized by greater surface charge charac-teristics than that of fresh crude oil. Certainly the oil/water interfacialsurface tension was much lower with the weathered versus fresh oil (11 vs. 25dynes/cm; see Table 2-10) and this did enhance oil droplet dispersion. Infact, it is quite possible that the more rapid decline in SPM loads with theweathered oils may be found in the relative dispersion rates for the three oilsinto the water column. Levels of dispersed oil (as measured by concentrations
3-19
SPM Concentrations vs. Timefor Different Starting Oil Types
70
60
0"- 5041,",="-cu 40
,a:..;;J
~ 30'0
0' c:E 20 0
fresh oilo
10
*--_._.-_._ ..-.* _.-._._.-. *_. 2 day weathered oil
_..-e.-.
12 day weathered oil.6,.
no oil->It--.
oo 20
.............~.... j" ···;····.,.·····'· ....1 .....•..• I • !
40 60 80 100 120 140 160 180 200 220
hours from start
Total Resolved Hydrocarbons--Dispersed Oil Phasefor Different Starting Oil Types
70
60
50"-~"- 40cua.
0 30C1'E
20
10
fresh oilo
2 day weathered oil_ .. _EJ-_ ..
12 day weathered oil....6,
//
./
a I • ! I ,!
o 20 40 60 80 100 120 140 160 180 200 220
hours from start
Figure 3-6. (a) SPM loads over time in experiments with fresh, 2-day weatheredand l2-day weathered Prudhoe Bay crude oil and with no oiladdition in the 28 liter stirred chamber system with continuousstirring. Exponential reg2ession lines are fitted to data pointsfor the three oil types (r > 0.89 for each line) and a linearregression line is fitted to-the data for no oil addition. Theenergy dissipation rate (~) ~n these experiments was estimated tobe approximately 260 ergs/em -sec for the duration of each experiment.
(b) Dispersed oil concentrations in the corresponding experiments withoil.3-20
of total resolved hydrocarbons) over time in the three experiments areillustrated in Figure 3-6b. The maximum concentration for fresh oil was notobserved until approximately 170 hours after the initial spill event. Incontrast, maximum concentrations with the 2-day and l2-day weathered oils wereobserved approximately 15-18 hours after the spill event. Consequently, thehigher levels of dispersed oil at early time points in the experiments with theweathered oils may have been responsible for the more rapid disappearance ofSPM from the water column.
In the experiments with 2-day and 12-day weathered oil, concentrationsof dispersed oil began to decline when SPM loads in the water column fell belowapproximately 25 mg dry weight per liter. Although at a much later time in theexperiment, a similar decline .in dispersed oil levels also appeared to occurwith fresh oil when the SPM load reached approximately 25 mg dry weight perliter. Huang and Elliot (1977) noted that the stability of oi1-in-water emul-sions can be dramatically affected by direct interactions between dispersed oildroplets and SPM particles. Specifically, SPM particles can associate with (or"coat") the oil-water interfaces of oil droplets due to surface charge proper-ties of both the SPM particles and the oil droplets. Such coatings of SPM canthen "armor the oil droplets against coalescence", thus increasing thestability of oi1-in-water emulsions (i.e., dispersed oil droplets). Thisincreased stability imparted to dispersed oil droplets can be directly relatedto absolute concentrations of SPM in a water column. For example, at SPMconcentrations either above or below some critical level, the stability of the"SPM-coated" dispersed oil droplets declines. At SPM concentrations below thiscritical level, the reservoir of SPM particles in the water column available tointeract with oil droplets is insufficient to adequately coat the oil dropletsto the degree necessary to enhance droplet stability. Under such circumstancesthe dispersed oil droplets would rise to the surface and recoa1esce into thesurface slick, rather than remain in the water column. This scenario couldexplain the declines in dispersed oil concentrations observed in all threeexperiments when SPM loads fell below approximately 25 mg dry weight per liter.Although not pursued in our experiments, Huang and Elliott (1977) note that thestability of dispersed oil droplet suspensions in the water column will alsodecline at high SPM loads (e.g., >200 mg/1iter). At these high SPM loads, thespecific gravity of oi1-SPM agglomerates will be increased (due to greater SPM
3-21
inclusions in the agglomerates) to the point that their specific gravity isgreater than that of the liquid medium. Thus, the oil-SPM agglomerates cansink out of the water column and thereby lower dispersed oil concentrations inthe water column.
3.2.2.2. Distribution of Oil Between Dispersed, Dissolved and SPM Phases in Ex-periments With Fresh, 2-day and l2-day Weathered Oil.
Concentrations of oil (measured as total resolved hydrocarbons) overtime in the dispersed. oil, SPM and dissolved phases in the experiments withfresh, 2-day and l2-day weathered oil are presented in Figure 3-7. In allthree experiments the majority of the oil in the whole water samples was alwayscontained in the dispersed oil phase. It must be noted, however, that the hy-drocarbon composition in the dissolved phase was always radically differentfrom that in the dispersed oil and SPM phases. Aromatic compounds were theonly hydrocarbons ever detected in dissolved phase samples. In contrast, ali-phatic compounds were consistently the most abundant hydrocarbons observed inthe dispersed oil and SPM phases of samples, although aromatic compounds werealso detected. As for relative concentration levels in those phases with asimilar predominance of aliphatic compounds (i.e., the dispersed oil and SPMphases), it should be noted that total resolved hydrocarbon concentrations on aper liter seawater basis were consistently greater in the dispersed oil phase.
It has been noted that only aromatic compounds were detected in thedissolved phases of whole water samples, whereas aliphatic components were dom-inant (although aromatics were present) in all samples of surface oil, dis-persed oil , and SPM samples that had either "settled out" or remained suspend-ed in the water column. The similar aliphatic character of the latter samplephases suggests that direct dispersed oil droplet-SPM interactions were theprimary route by which the oil hydrocarbons became associated with the SPMparticles.
3.2.2.3. FID-GC Analyses of Oil Fractions in the SPM and Dispersed Oil Phasesof Experiments in the 28 Liter System.
In a manner analagous to that described in the preceding sedimentationexperiments, compound specific differences were investigated in the dispersed
3-22
Total Resolved Hydrocarbon ConcentrationsFresh Oit
1.41.31.21.1
"- 1.0lU.-::: 0.9"-lU 0.8a.
'0 0.7C7' 0.6E
0.50.4
0.30.20.10.0
0 20 40 60 80 100 120 140 160 180 200 220hours from start
Total Resolved Hydrocarbon Concentrations2 Day Weathered Oil
1.41.31.21.1
"- 1.0lU~ 0.9"- 0.8lUa.
'0 0.7
C7' 0.6E 0.5
0.4-:
0.30.20.10.0
0
/ ", __G..,e- _--~~.~a~~-~~~---------------{3-- - - - - - - - - - - - - - - - - --EJ
£:i.'6.8
·····················6010 20 30 40 50 60 70 80
hours from start
dispersed (X 1/30)o
dissolved----9---
SP~A
dispersed (X 1/.30)o
dissolved----E}---
Figure 3-7. (a) Concentrations of oil (i.e., total resolved hydrocarbons) overtime in the dispersed oil, dissolved and SPM phases of wholewater samples from experiments with Prudhoe Bay crude oil inthe 28 liter stirred chamber system. The energy dissipation rate(E) in She experiments was estimated to be approximately 260ergs/em -sec. Fresh Prudhoe Bay crude oil.
(b) Comparable information with 2-day weathered oil.
3-23
Total Resolved Hydrocarbon Concentrations12 Day Weathered Oil
...Q,).•..
1.41..31.21.1
1.0
0.9
0.80.70.60.50.40 . .3
0.2O. 1 '.-: 'J:lc c~ ~~~~~~~~__-.e- ----~~.• ~'77~~~ ~~~_~~__~: _.- •• - •• -' -' _---EJ
0.0o 10 20 .30 40 50 60 70 80 90 100
hours from start
dispersed (X 1/50)o
dissolved----9---
SPM8.
Figure 3-7. (c) Comparable information with l2-day weathered oil.
...Q,)a.
'0C7'E
3-24
and SPM phases of samples collected during experiments in the 28 liter system.Similar compound specific trends to those reported in section 3.2.1.1. were ob-served. For example, Figure 3-8 illustrates absolute concentrations (per gramdry weight) of individual n-alkanes and aromatic compounds in SPM that had"settled out" of the water column as well as SPM that remained suspended at73.5 hours after the spill event in the experiment with 2-day weathered crudeoil. Much higher concentrations of both the n-alkanes and aromatics were ob-served in the "sedimented" SPM. Furthermore, ratios of the specific compoundsto nC2l (Figure 3-9) indicate a distinct relative enhancement of both the lowmolecular weight n-alkanes and the aromatic compounds in the SPM fraction thathad "settled out" of the water column.
3-25
In both the sedimentation and large volume stirred chamber experiments(Sections 3.2.1. and 3,2.2., respectively), it is noteworthy that hydrocarboncompositions in SPM that "settled out" of the water column had compound speci-fic compositions that more closely resembled that in the dispersed oil asopposed to the "residual suspended" SPM remaining at the end of thesedimentation experiment. Because SPM that "settles out" originates from theinitial SPM in the water column, one might expect "settled" bottom sediment tohave a similar oil composition to that of the "residual suspended" SPM. Resultsfrom both the sedimentation and large volume stirred chamber experimentsindicate, however, that "sedimented" oil (i.e., that which could be transportedto bottom sediments in natural environments) might be less subject todissolution losses of lower molecular weight compounds than would be expectedfrom hydrocarbon compositions in particulate phases that remain suspended.Microscopic examination of sedimented oil/SPM agglomerates has suggested thatthe larger flocs of oiled SPM contain discrete 5-10 ~m oil droplets that areless subject to lower molecular weight compound dissolution (compared to thinoil coatings on residual SPM) due to their lower surface to volume ratios.This subject was not be pursued further due to limitations of funds and thedesire to pursue phenomena that could more readily be modeled. Although suchchemical partitioning has not been modeled to date, it may have particularrelevance for predictions of effects of oiled particulate phases on benthicfauna.
Sediment Concentrations: n-alkanes2 Day Weathered Oil--28 Liter System
73.5 Hours Post-Spill
9
2.42.2
::E 2.0a..(/) 1.8'0 1.6.;,. 1.4e"'0 1.2E 1.0o'-0-<, 0.8Ec 0.6'-0-
E 0.40.20.0
Sedimented SPM
Suspended SPM·······0···
10 12 14
~.o·O·~··a ...o···~··O~OG.Q ...
···0·········
16 18 20 22 24 26 28 30 32n-alkane carbon number
SPM Concentrations: Aromatics2 Day 'Weathered Oil--28 Liter System
73.5 Hours Post-Spill
700
E 300o'-0-<,E 200o'-0-::J
600_ Sedimented SPM
~ Suspended SPM::Ea..(/)
-- 500o
100
3-26
of\OP'" 2_",e~o ",e~o d'",e~o d'",e~o '",e~o p",ef\
v- ,,3- \ ',2- \ 2,3,6-tfl
Aromatic Compound
Figure 3-8. (a) Absolute concentrations of n-alkanes associated with"sedimented" and "residual suspended" SPK fractions at thefinal sampling time in the 28 liter stirred chamberexperiment with 2-day weathered Prudhoe Bay crude oil.
(b) Comparable concentrations for selected aromatic compounds(napth naphthalene; see Figure 3-4 (b) for other compoundidentification) .
Ratios: nC(X)/nC212 Day Weathered Oil--28 Liter System
73.5 Hours Post-Spill
2.22.01.81.61.4
0 1.2.•...0•... 1.0
0.80.60.40.20.0
eI~'\, '
,/ 'l! -&- .•.~. ,rai \· ,· ,· ,· .: Q· ,· "· ,
,/ t'2 -,. ,
~.i,\ .,~_ .••.••..••.....A.~.,
.1>."6' ~"A-....::;•."~1.
,\
\&:. AA
dispersed oil
sedimented oil----90---SPM oil
....... 1>....
, -.\, "';0.
G-.s...10 12 14 16 18 20 22 24 26 28 30 32
n-alkane carbon number
Rotics: Aromatic Cmpd./nC212 Day Weathered Oil--28 Liter System
73.5 Hours Post-Spill
0.6~ Dispersed oil
IISedimented SPM
~ Suspended SPM
0.7
0.5
0.40
:;J0•...
0.3
0.2
0.1
0.0
Aromatic Compound
Figure 3-9. (a) Concentration ratio information for n-alkanes to ne2l
fro.the experiment in Figure 3-8.
(b) Comparable information for aromatic compound ratios inFigure 3-8.
3-27
3.3 PARTITIONING OF DISSOLVED PETROLEUM HYDROCARBONS BETWEEN SEDIMENT ANDWATER
When a chemical compound becomes dissolved into water in the presenceof suspended particulate matter, a portion of the compound will adsorb onto theparticulates. The extent to which this adsorption takes place is typically de-scribed by an adsorption isotherm, such as the Langmuir equation, the BET equa-tion, or the Freundlich equation. In natural systems, however, the adsorptivecapacity of the solids is invariably orders of magnitude greater than the solidphase concentration (O'Conner and Conno1y, 1980). Under these (dilute) condi-tions the equilibrium concentrations of the compound in the aqueous and solidphases are related by,
KP
Cs
Cw
solid phase concentrationaqueous phase concentration
where K is called t4e partition coefficient. The magnitude of this coeffi-p
cient depends on the characteristics of the compound and the adsorbing solids.
The experiment described below was performed in order to measure thepartition coefficient of hydrocarbons present in Prudhoe Bay crude oil.
Experimental Procedure
"Oil accomodated seawater" was prepared by placing one liter of un-weathered Prudhoe Bay crude oil and one liter of seawater into a separatoryfunnel. The funnel was then allowed to equilibrate for several days.
The sediment utilized for the experiments was obtained from the upperintertidal zone of Jako1of Bay. This sediment was initially filtered through a54 ~m geological sieve and then allowed to settle in a beaker for approxi-mately 2 1/2 hours. The settled sediment was saved, the aqueous phase discard-ed.
A 300 m1 aliquot of the "oil accomodated seawater" was vacuum filteredthrough a 0.4 ~m pore size polyester filter to remove small dispersed oil
3-28
droplets. Approximately 1.02 grams of sediment was then added to the water ina separatory funnel. The mixture was then allowed to equilibrate for 12 hours.Occasionally, the separatory funnel was agitated to resuspend the sediments.
After equilibration, the settled SPM (at the bottom of the separatoryfunnel) was carefully removed onto a polyester filter. The aqueous phase wasvacuum filtered through another filter and then extracted twice with 100 ml ofmethylene chloride. The filters then received vacuum filtrations of the fol-lowing solutions 1) tapwater, 2) 10 ml methanol, and 3) 30 ml methanol chlo-ride. These filtrates were collected in a separatory funnel, partioned against100 ml of seawater, and the remaining aqueous phase extracted with 100 ml ofmethylene chloride.
The resulting extract (of the aqueous and particulate phases) werereduced in volume and analyzed by FID-GC.
Experimental Results
The results of partitioning experiment are presented in Table 3-2.Additional compounds (not listed in Table 3-2) were detected in one phase butnot the other. This fact is due to the detection limits of the GC and to thepartitioning behavior of the hydrocarbons. The measured partition coefficientsrange from 4.1 to 380.
Implications for Suspended Particulates
The results above can be used to calculate concentrations of aromatichydrocarbons in suspended sediment of the type used with the conditionsemployed in the experiment. Additional studies with dissolved components fromdifferent true boiling point (distillate) cuts of Prudhoe Bay crude oil and avariety of other SPM types are being continued.
3-29
Table 3-2 Partitioning Experiment Results.
Retention Time(min)
Water phaseconcentration (J.lg/g)
Sediment phaseconcentration (JJg/g)
Compound J.D. Panitioncoefficient, K
4.88 toluene 1.16.1 5.57.84 ethyl benzene 0.067 0.84 12.58.17 m, p-xylene 0.21 2.7 12.99.10 o-xylene 0.14 0.57 4.110.79
0.004 0.55 "138.22.24 naphthalene 0.026 0.69 26.526.99 2-methyl naphthalene 0.005 1.9380.27.68 I-methyl naphthalene 0.016 1.487.5
31.950.053 0.67 12.6w
I
..
W0
4.0 MODELING OF PHYSICAL PROCESSES INVOLVED WITH THE INTERACTION OF OILDROPLETS AND SPM IN THE WATER COLUMN
4.1 WATER COLUMN PROCESSES
The modeling of the advection, mixing and interaction of oil dropletsand SPM in the water column requires the consideration of a number of inter-acting physical processes. If the problem is reduced to predicting the dis-tribution of oil and SPM concentrations, without considering interactions, thenonly the inputs of material from oil spills at the surface and from resuspen-sion of sediment from the bottom need to be defined and modeled. The interiorwater column advection and mixing are described by the three-dimensional massconservation equation which determines the concentrations as functions of spaceand time. Oil and SPM occur in the water column with size-class distributionswith the smaller oil-droplet and sediment grain sizes predominating. This isbecause fine-grain sands and silts are more likely than coarse sands to beresuspended from the bottom under the action of bottom currents, and smalleroil droplets seem to be more readily dispersed into the water column from sur-face oil slicks (Bouwmeester and Wallace, 1986). Even if there is no inter-action between particles, the non-linear form of the mass-conservation equationand the dependence of the sinking (rising) velocity on the particle size and
(buoyancy) means that each size class requires a separate equation.illustrated by the one-dimensional mass conservation equation (i.e.
neglecting horizontal advection and mixing) for the concentration of SPM, C.,~
densityThis is
with mean diameter d.;~
ae. ae.~ ~a + (w + wfi) azt'
o (4-1)
where w is the vertical fluid velocity, v is the vertical turbulent eddytsdiffusivity, wfi is the fall velocity of the particle, usually given by Stoke'sLaw (equation 5-11), and z is the vertical coordinate, + upwards. This equa-tion (4-1) is applied separately to each size class of particles and oil drop-lets present in the water column. If the particles interact through coagula-tion and floculation then an interaction term, Ri, must be included on the
4-1
right hand side of equation 4-1. This term, Ri, represents the source ofparticles due to the coagulation of particles of different smaller sizes toproduce a particle of effective diameter di and the break-up of larger particleconglomerates by turbulence to produce particles of size class, i. It alsorepresents sinks due to coagulation of particles of size class i with otherparticles and the break up of particles which remove them from size class i.The interaction of particles is usually approximately modeled by kinetic rela-tionships similar to those discussed in Sections 1 and 2. Thus, if even only afew size classes, i,are modeled, the deterministic bookkeeping on particleconcentrations in each size class becomes quite complex. In recent years astochastic approach to modeling the transport of interacting particles of mul-tiple size classes has been proposed and used successfully to model coagulationprocesses (Mercier, 1985) and turbulent reacting flows (Pope, 1979; 1981;1982). This method is discussed in more detail below.
A schematic of the processes acting in the water column is shown in Figure4-1. In simplest terms SPM is input from the sea bed by the bottom boundarydynamics (or riverine sources which are not explicitly discussed here) and oildroplets are input from the oil slick by surface layer processes. Both inputconditions involve surface waves and wind. The physics of bottom boundarylayer are quite well understood due to the theoretical models of Grant andMadsen (1979, 1982) and involve the non-linear interaction of surface waveoscillatory currents with steady or low-frequency currents (i.e. tidal or windforced) in the bottom boundary layer. The entrainment of oil by the action ofwaves and the wind driven surface turbulent boundary layer is not well under-stood. Most of the evidence comes from wind tunnel and flume experiments(Bouwmeester and Wallace; 1985; 1986) where there are problems of consistentscaling for the turbulence and the waves compared with the ocean. However,there is indication that the turbulence introduced by breaking waves facili-tates the production of small oil-droplets beneath a slick. There have beensome attempts to model the formation and depth of penetration of.oil dropletsdue to breaking waves (Aravamudan et al., 1982; Mackay et al., 1982) but thedevelopment of a solid theory is limited by the lack of knowledge and quantifi-cation of turbulence generated by breaking waves.
4-2
Water Column
Wind Stress Oil Spill
Turbulence• Wave Mixing• Wave Breaking
J J J Oil Droplets forced intowater column by wave
breaking and windVelocityProfile
Advection• Salinity• Temperature• SPM• Oil Droplets
Turbulence andStratification
EffectsChemical Kinetics and
Particle to Particle Dynamics
Wave andCurrent BottomBoundary Layer
TurbulenceGeneration andBottom Friction
Resuspension ofSPM by BottomBoundary layer
Dynamics
Figure 4-1 Sketch of water column processes affecting the distribution ofoil and SPM.
4.2 BOUNDARY CONDITIONS
As far as the model of advection and mixing of oil and SPM in the watercolumn is concerned, the boundary submodels provide the flux of material to thewater column. This is expressed as
acv = F at z - zts az T (4-2)
where F is the vertical flux, 'usually expressed as a vertical velocity multi-plied by a concentration, and zT is a level just below the surface or justabove the bottom. The concentrations; C, and the turbulent diffusivity of theinterior and boundary layer models should match at z - zT' In addition for thebottom boundary layer model the current velocity, u, and the turbulent viscos-ity, vt' should also match the interior circulation model at z = zT (seeSection 5 for details). Equation 4-2 provides the boundary conditions forequation 4-1 or its 3-D equivalent assuming a level bottom.
The physical processes that resuspend sediment are as follows: the nearbottom oscillatory currents generated by surface waves combine with the lowfrequency currents in the bottom wave-current boundary layer to enhance bottomfriction above that felt by a steady current alone. The enhanced bottomfriction has two effects: the first is to increase the skin friction on thebed so that sediment grains are more readily placed in suspension, and thesecond is to increase the turbulence and hence the eddy viscosity and diffusiv-ity in the boundary layer.
If the shear stress on the bed initiates sediment motion, then this movingbed under the action waves and steady currents has the effect of furtherenhancing the effective bottom friction. The initiation of sediment movementis dependant on the grain size of the sediments. Thus, smaller particles aremore readily moved than larger particles. Once in motion particles can bemixed upwards by the turbulence in the boundary layer. Boundary layer turbulentmixing is proportional to the bottom shear stress velocity. This, in turn is a
4-4
function not only of the skin friction but of friction due to the larger scalebedforms such as ripples or bed formations due to biological activity. Sedimentin motion near the bed which is not mixed up into the boundary layer is knownas bedload transport, and its presence introduces density stratification veryclose to the bottom which· has the effect of suppressing the mixing. Thus,there are a number of competing effects in the calculation of sediment trans-port and vertical SPM flux to the water column. These account for the complex-ity of the iteration procedures used to calculate the initiation of sedimentmotion, bottom boundary layer turbulent coefficients and SPM flux in the Grant,Madsen and Glenn model described in Section 5. The major limitation of thistheory is that it only applies to non-cohesive sediments such as sand. Thereis currently no equivalent theory for cohesive sediments, and thus this bottomboundary layer model should be used with care when even small amounts of claysare present in the bottom sediment. A review of bottom boundary layer dynamicsand models is given by Grant and Madsen, (1986).
Surface boundary layer turbulence and mixing under the combined effects ofwind, waves and background currents is not well understood. Surface waveswhich are not breaking are not turbulent since the wave velocity field isirrotational. In the bottom boundary-layer it is the interaction of the wavecurrents with the bottom in the wave boundary layer that generates turbulence.Thus breaking waves are required to inject oil and turbulent energy below thesurface. Most of the studies on this problem have been done in wind-waveflumes where incompatibilities of the scaling of wave motion (by Froude Number)and turbulence (by Reynolds Number) make application to the ocean surfaceuncertain. The principal result of the laboratory studies of Bouwmeester andWallace (1985, 1986) was that small oil droplets (25~m diameter) predominate inthe water column due to dispersal from a surface oil slick by breaking waves.Larger droplets tend to return to the surface due to buoyancy. There do notseem to be any systematic studies of oil entrainment rates as functions ofsea-state, composition and age of the oil. Clearly the rate of breaking of thesteepest waves will determine the rate of input of oil droplets to the surfacelayer. This can be estimated from wave spectra (Longuet-Higgins, 1969). Thisimplies a certain intermittency in both space and time by the entrainment mech-anisms. Note that breaking waves are in the short period part of the spectrum
4-5
(i.e. wind-waves), whereas waves that generate bottom turbulence correspond tolong waves (i.e. swell) that have wavelengths greater than half the waterdepth. Thus, both sea and swell (i.e. the complete wave spectrum) are requiredto generate input data for both top and bottom boundary conditions. There areno current formulations which satisfactorily describe the flux of oil dropletsfrom a surface slick to the water column due to wind and wave action. As aresult, further laboratory experiments on this problem are being conducted byDelft Hydraulics Laboratory under a separate MMS contract. A literature reviewby Delvigne et al., (1986) discusses some possible formulations for calculatingdissipation rates and eddy viscosities due to intermittently breaking waves.
4.3 WATER COLUMN PROCESSES
The mixture of oil droplets and SPM in the water column is acted upon bythe advection and turbulence of the fluid, and it undergoes transformations dueto coagulation. The simplest possible model of oil and SPM transport wouldconsist of three equations similar to 4-1, one for oil droplets of similardiameter, one for SPM of a single size class and one for oil-SPM agglomorates.Only disimilar particles could interact. Thus, the coagulation of oil dropletsto form larger droplets or the coagulation of SPM particles or oiled-SPM par-ticles would be prohibited. This, of course, does not happen in natural envi-ronments, so such an approach is only likely to be approximately true for verylow concentrations of oil droplets with SPM containing no clays or organicmatter (i.e. fine sand grains) so that SPM particles are unlikely to sticktogether even if they collide. As noted, this is not very realistic, and ifreactions are allowed to occur, then different ranges of size classes for oildroplets, SPM and oiled-SPM are required. Solving a large number of equationsof type 4-1 with complex source and sink terms for each particle class quicklybecomes prohibitive in computer costs (Pope,198l). Alternative methods usingMonte Carlo techniques to solve the transport equation for the joint probabil-ity density function (pdf) for particle concentrations has proved effective forreacting constituents in a turbulent fluid (Pope, 1979;,1981). Mercier (1985)applied Pope's methods to modeling the transport and dispersion of sewagesludge from an outfall including coagulation of the particles and settling.
4-6
It is not the purpose of this section to present the theory and solutionmethods for the pdf transport equation, but rather to indicate thatconventional finite difference or element methods are impractical if thereactions (coagulation) between different particle size classes and differentparticle-types are to be treated in a reasonable manner. The details of thepdf transport equation, coagulation formulations, and the Monte Carlo solutionmethod, which should be readily adaptable to the oi1-SPM problem, are given byMercier (1985). However, brief descriptions of the concepts behind the sto-chastic pdf transport model and the mechanisms that promote coagulation in aturbulent fluid, are presented in the following paragraphs.
The control volume of a finite difference transport model has horizontaldimensions of the order of a few kilometers and depth of a few meters. Theturbulence length scale which is the Ko1mogorov length scale, )(approximate1y1 rom to 1 cm) defines the smallest volume element that is completely mixed.The joint pdf for a particular control volume is represented by an ensemble ofN elements, each of which "contains" separate representative concentrations ofeach constituent. Elements can be considered as approximately equal-sized,completely mixed, lumps of fluid, with characteristic length and time scalesgiven by the turbulence scales. The Monte Carlo method manipulates theensemble of elements so as to simulate the corresponding evolution of the jointpdf which is governed by the pdf transport equation. Thus, the statistics ofthe ensemble are equivalent to the statistics of the pdf. The result is thatthe mean concentration of a constituant over N elements is equivalent to themean concentration of that constituent in the control volume such as might bedetermined by a conventional equation 4-1. Each control volume is spatiallyuniform or equivalently homogenous from a statistical perspective. Therefore,the element volumes have no relative position within the volume. The elementset represents typical constituent concentrations that one would obtain if Nsamples, with volumes of order )(3 were taken at random points throughout theassumed homogenous control volume.
The Monte Carlo technique simulates the effects of that physical processesof advection, turbulent mixing and settling have on the ensemble of elements ineach control volume as well as the effects on the ensemble of
4-7
g(d) -4Ad (2~m < d < 100~m) (4-3)
reactions in "composition" space. One of the advantages of this pdf approachis that the source and sink term, Ri, does not have to be specifically modeled(i.e. it appears in the equation in closed form Mercier, 1985; Pope 1979;1981). The distribution of particle sizes in natural waters is approximatedby:
where g(d) is the number of particles per unit fluid volume of diameter d and Ais a constant (Mercier, 1985). Therefore particles at the lowest end of thesize range tend to predominate. The coagulation of particles depends upontheir collision rate. Mechanisms which cause particles to collide are Brownianmotion, fluid shear and differential sedimentation. Collision rates, derivedby assuming rectilinear motion of particles, are modified by fluid shear gener-ated by the motions and short range attractive van der Waals forces and repul-sive electrostatic double-layer forces. These are taken into account by colli-sion efficiency functions which modify the collision rates for the variousmechanisms. Mercier (1985) discusses the formulation for the collision fre-quencies due to the three mechanisms and solves the equations numerically. Heshows that coagulation by all three mechanisms is dominated by particles of thesmallest size. Thus, larger particles are more likely to collide with smallerparticles than with particles of similar size. The coagulation equations canbe incorporated into the source terms of the pdf transport equation and solvedusing Monte Carlo techniques for transport through composition space (i.e.changes in number density of particle size classes due to coagulation).
This section is very brief introduction to the complexities of modelingreactive transport of suspended particles. The reader is referred to Mercier'sThesis for a more complete and rigorous discussion.
4.4 COMPONENT MODELS OF OIL-SPM TRANSPORT AND FATE
The previous sections have discussed surface and bottom boundary layer andwater column processes affecting the modeling of the interaction and transportof oil and SPM. However, to construct a model of oil-SPM transport, hori-
4-8
zontal spacially varying processes need to be considered as is indicated by thesketch in Figure 4-2. Thus a coastal sea model will have open boundaries forwhich deep ocean conditions need to be prescribed. This includes tides, spec-ification of salinity, temperature and SPM concentrations at minimum. A fullythree dimensional circulation model is required to predict the velocity fieldwhich advects the constituents in the 3-D transport model. Current velocitiesand winds will move and disperse the oil slick at the surface. Other inputsinclude river sources of brackish water and SPM, and SPM input from coastalerosion. Finally the surface wave field including deep water swells as well aswind seas for input to the bottom boundary layer sediment resuspension modeland the surface wave-breaking mi~ing model will be required.
The model components of a complete 3-D oil-SPM transport model arerepresented by the box diagram in Figure 4-3. The space dimensionality (1, 2or 3-D) and physical basis of each model component are indicated. Thus, "massconservation" indicates that the major equations of this component are derivedfrom the law of mass conservation (i.e. equation 4-1) and "dynamical" meansthat momentum conservation equations (i.e. the prediction of current veloc-ities) are required. All models and external inputs are assumed to be timedependent. The arrows indicate the transfers of information between modelcomponents.
It can be seen that the 3-D circulation model is the central component inthat it supplies velocities and mixing coefficients to most of the othercomponents which in turn supply boundary conditions. There is a requirementthat surface and bottom velocities as well as turbulent coefficients match atappropriate levels within the boundary layers. Thus, the interactions betweenthe boundary sub-models and the circulation model are essentially non-linear.The 3-D circulation model will usually predict salinity and temperature fieldsbecause horizontal density gradients modify wind-forced currents and verticaldensity gradients (stratification) suppress the turbulent mixing processes.
Since the surface wave model needs to calculate low frequency (i.e. swell)waves for the bottom boundary layer model, it may cover a much larger area thanany given coastal circulation model. Thus a model of Norton Sound
4-9
Model Open Boundary(Tidal Input)
••SurfaceWaves
Plan View
~ WIND 3-D Advection andMixng of Salinity,
Temperature. SPM.Oil and Oiled-SPM
Figure 4-2 Sketch of a plan view of oil-SPM transport processes.
Current Velocities
Riverine Input of SPM andBrackish Water
4-10
<Etherl~
~Surface Wave 2-D
Ptetlciton
DYNAMICAL
OlbIIaIWaw
VeIociIles
Bottom 1-0,t.ayer
}- •• ~ SedmentResuspensJon
DYNAMICAL
OiJ.SPMIntefBctlonKinetics
C) = ExternalForcing
Figure 4-3 Component Models of a 3-D Oil-SPM Transport Model
Waw BreakingSurface Oil 2-D
Model
MASSCONSERVATION
Mixing
AdvedlveVelocltlea &
Mixk1gCoefficients
Boltom FrictionCmJIat/on
Model
DYNAMICAL .ndMASS
CONSERVAnON
MIxk1g Coefficient
Boltom CUl'nlflts
AdvedlveVelocltles &
Mixk1gCoefficients
1·D
3-D
01 Droplets toWater Coh.mn
would probably require a wave prediction model that includes the deep water ofthe Bering Sea. An example of a parametric wave prediction model is given byGunther et al., (1979) and a recent review of wind-wave prediction models isgiven by Sobey (1986). If the oil-SPM model is used in a hindcast mode thenwave spectra, preferably directional, could be obtained from offshore wave-rider buoys and (with assumptions on uniformity) directly input into theboundary layer models.
As a result of these analyses, it now appears that it may be more appropriateto use the pdf formulation of the transport equation (solved by Monte Carlomethods discussed above) for the oil-SPM transport model. This would espe-cially to be case if the model is to include representative size classei of oildroplets and SPM as well as different coagulation mechanisms. For this reasonas well as the complexity of the boundary conditions, the Oil-SPM transportmodel should probably be a separate model from the circulation model eventhough the circulation model provides the 3-D velocity and turbulence fields todrive this model.
The complete oil-SPM transport model as represented by Figure 4-3 does notexist and not all components have satisfactory models at present. Even thoughthe bottom-boundary layer model, described in detail in the next section, isnow well established it has not yet been incorporated into continental shelfcirculation models. The stochastic transport model for reactive particles is acompletely new technique for oceanography. Formulations for surface layermixing due to wave breaking and Langmuir circulations are not well established.Therefore it is recommended that the development of the model proceed instages. Possible development scenarios are as follows:
1. Incorporate Grant/Madsen bottom boundary layer model for bottom fric-tion into 3-D circulation model. Determine effects on wind-drivenflow for storm conditions. Spectra from wave-rider buoys could beused as input.
2. Attempt application of parametric wind-wave/swell models to areas ofinterest. When possible, use hindcast wave conditions for specificstorm events to evaluate modeled wave spectra using wave-rider data.
4-12
3. Develop stochastic oi1-SPM reactive transport model based on Mercier(1985) in simple 1-0 form and apply to Kasitsna Bay Laboratory experi-ments to test the realism of the coagulation formulations.
4. Formulate, and devise laboratory tests for a model of the generationof oil droplets (including size distribution) from an oil slick bywind and breaking waves.
S. Develop projects 3 and 4 along with the bottom boundary layer/sedimentresuspension model for a 1-0 (depth) model of the water column underan oil slick. Horizontal uniformity of depth, current velocity, wavefields and bottom characteristics would be assumed and motion would berelative to the oil slick (i.e. the coordinate system would be fixedin the oil slick.) Surface wave data could be obtained from project 2or from wave-rider. This model would in effect be a 1-0 version ofthe complete oi1-SPM transport model (Figure 4-3). It would allow theinteractions of the component models to be properly incorporated andexperimented upon, without being prohibitive in computer costs. Thelimitations and approximations due to the 1-0 assumption should not beunduly restrictive.
6. Develop 5 into complete 3-D model incorporating the 3-D circulationmodel and expanding the stochastic transport model to 3-D. This modelmay require extensive super computer resources even for a relativelysmall area such as Norton Sound.
4-13
5.0 APPLICATION OF THE GRANT-MADSEN BOUNDARY LAYER MODEL TO A MODEL OFSUSPENDED PARTICULATE TRANSPORT
5.1 INTRODUCTION
The Grant-Madsen-G1enn boundary layer model provides a method for es-timating bottom stress in the presence of waves and currents, including treat-ments of movable bed roughness, initiation of sediment motion, sediment suspen-sion, and stratification by suspended sediments. The foundation of the work isthe treatment of waves in the presence of a steady current, presented by Grantand Madsen (1979). The theory divides the near-bottom boundary layer into tworegions: 1) a thin layer, typically two to twenty centimeters thick, in whichthe energy of the eddies is controlled by the wave motion, and 2) a broader re-gion, with a thickness on the order of meters, where the eddy energy is relatedonly to the non-oscillatory part of the current. Using this assumption, thebottom shear stress is calculated, and eddy viscosities are determined for thetwo regions. These are used to predict near-bottom velocity profiles undercombined wave and curre~t flows.
Another component of ~he present model is the movable bed roughnessmodel of Grant and Madsen (1982). It predicts the physical boundary roughnessdue to bedforms and moving sediment, which depend on the skin friction shearstress generated by the flow. The bed roughness model contributes to the esti-mate of total shear stress by modifying the effective drag coefficient of thebed.
The application of the Grant and Madsen model to sediment transportwas performed by Glenn (1983) and Grant and Glenn (1983a). This model uses theGrant-Madsen (1979) wave-current interaction model and the Grant-Madsen (1982)bed roughness model, in combination with empirically derived relations for ini-tiation of sediment motion and semi-empirical models of near-bed suspended sed-iment concentration, to represent the vertical distribution and transport ofsuspended sediment in conditions representative of the continental shelf. Themodel includes the damping influence of stable stratification by suspended sed-iment on turbulence in the boundary layer, with consequent reduction of meanboundary shear stress under certain conditions. They also developed a fullEkman layer model under waves and currents. The near-bottom model is currently
5-1
being applied explicitly to sediment transport problems by a student of Grantand Madsen, Margaret Goud. She has added a bedload transport estimate and anestimate of load and transport in the outer Ekman layer, and has investigatedthe uncertainties in sediment load and transport predictions based on the as-sumptions in the model.
The fundamental advance by Grant and Madsen was the 'treatment of wavesas they affect boundary layer flow, which is critical for prediction of sedi-ment transport on the continental shelf. The Grant-Madsen-G1enn sedimenttransport model (hereafter referred to as GMG) combines this representation ofwave-current interaction with a combined theoretical and empirical represent-ation of the sediment dynamics to yield a relatively simple but powerful pre-dictive model of sediment transport. However, it should be emphasized that theGMG model is only applicable where the effects of breaking waves (e.g., thesurf zone) do not penetrate to the bottom boundary layer. The GMG model wouldhave to be modified to be useful when water depths are less than approximately3-4 wave heights (i.e., the depth at which breaking waves "penetrate" to thebottom).
The following discussion will provide a brief synopsis of the elementsof the Grant~Madsen-G1enn model, with emphasis on the application of the modelas the boundary condition to a circulation-transport model. The discussion isby no means comprehensive, and the reader is referred to the three technicalreports prepared by Grant and Glenn (1983a,1983b,1983c) for a complete treat-ment of the derivation of the theory, discussion of the assumptions and uncer-tainties, and the solution procedure, including Fortran code.
In Section 5.2, the relevant fluid and sediment dynamics will be dis-cussed, followed in Section 5.3 by a flow chart of the model, with examples ofresults. Section 5.4 will be a discussion of the model's uses and limitationsas an element of a numerical model of continental shelf sediment transport.
5.2 MODEL ELEMENTS
5.2.1 Boundary Layer Hydrodynamics
5-2
The bottom boundary layer is the region of the flow that is signifi-cantly influenced by bottom stress, which may be limited to a small fraction ofthe water column, depending on the water depth, the strength of the flow, andthe time scales of motion. A boundary layer can be described most effectivelyby a length scale, S which represents the height of the boundary layer, and avelocity scale, u*. The so-called friction velocity u* is defined by:
u -*where TO is the bottom stress and p is the fluid density. By scaling the mo-mentum equation, it can be shown that
u*d - 0(-)w
where 0 means "on the order of" and w is the dominant frequency of motion,which may be the orbital frequency of waves, the tidal frequency, or theCoriolis frequency, f, depending on the flow.
Because surface gravity waves have frequencies far higher than tidesor geostrophic currents, the boundary layers associated with them are orders ofmagnitude thinner. In environments where there are significant currents aswell as surface waves, it is convenient to divide the boundary layer into tworegions, a narrow region that is strongly influenced by the waves and relative-ly weakly by the current, and a broad region that is influenced only by thecurrent. The length and velocity scales of the "wave-current" boundary layerare designated Sand u* and those of the "current" boundary layer are de-cw cwnoted Sand u* .~ c
The turbulence in the wave boundary layer will thus tend to be moreintense than that in the current boundary layer, principally because of thestrong vertical velocity gradients associtaed with the small vertical lengthscale of the wave boundary layer. Thus the velocity scale u* will often becwmuch larger than u*. It should be pointed out, however, that u* is associ-c cw
5-3
ated with an oscillatory stress, and the mean stress, reflected in the value ofu*c is essentially constant across the wave-current boundary layer.
It has long been recognized that the turbulent flux of momentum can berepresented effectively in the turbulent boundary layers by coefficients of ed-dy viscosity vt of the form
where ~ is von Karman's constant (~ - 0.41) and z is the vertical distance fromthe bed. This formulation leads to the familiar logarithmic velocity profilein the vicinity of the bed. The Grant-Madsen (1979) formulation assumes thisform for the eddy viscosity in order to solve for the flow in the wave-currentand current boundary layers. Although the details of the oscillatory boundarylayer flow are not of interest in a model of the low-frequency currents, thewave motions largely determine the value of u* and a solution for the osci1-cwlatory boundary layer-motion is required to establish the value of u* givencwthe wave and current parameters. Based on arguments about the nature of turbu-lence production in boundary layers, Grant and Madsen (1979) define
r r 1/21-£ + w,max,p p
where rand r are stress components due to the mean and the wave components,c weach of which includes the interaction terms between the currents and thewaves.
The expression for r is obtained by solving for the oscillatory ve-wlocity, and using the closure relation
rw
to obtain an expression for r in terms of u* and the wave parameters. Anw cwfor r is obtained by defining a friction factor f using a qua-c cwexpression
dratic drag law:
5-4
1-2Pf lulucw
where TO is the mean bottom shear stress and u is a representative velocity inthe wave-current boundary layer, time-averaged over the wave period. T andcu*cw are each written in terms of the mean and wave-induced currents and thefriction factor. These expressions are combined to yield an implicit expres-sion for f ,which is then used to solve for u* and u* .cw cw c
The derivation of the solution for the friction factor, and thereforethe shear velocities, is more involved than this discussion warrants; it is de-tailed in Grant and Madsen (1979). The solutions for the wave velocity and thefriction factor are included in a short appendix to this report. It should bepointed out here that u* and u* depend on the orbital velocity of the domi-c cwnant waves, the wave frequency, the mean current velocity in the boundary lay-er, the relative angle between the waves and currents, and the bottom roughness(see appendix for formula). The mean velocity in the boundary layer, repre-sented by the symbol u , is used as an iteration parameter, starting from an
ainitial estimate or guess, with the iterations ending when the velocity at areference level z above the wave boundary layer matches the value determined
rfrom the model of the overlying flow.
The mean velocity profiles in the wave-current and current boundarylayers,are solved by assuming steady flow and constant stress, so that:
aucv (---) - lu lut,cw az *c *c zo < z < 6cw (5-1)
aucv (---) - lu lut,c az *c *c 6 < z < zcw r(5-2)
where
vt - ~u* z,cw cw z < 6cw (5-3)
5-5
II t,c z > Scw (5-4)and
s cwleU2 *cw
w (5-5)
The solutions to these equations are simply:
1 u*c zu(z) - -u (--)In-Ie *c u*cw zo z < Scw (5-6)
1 zu(z) - -u In-Ie *c zOc
z > S cw (5-7)
where Zo is the roughness length, the calculation of which is discussed below,and zOc is the apparent roughness length of the outer flow, defined by
(5-8)
which is obtained by matching the solutions at S . Note that the effect ofcwthe wave on the flow above the wave boundary layer is an increase in the rough-ness length zOc; u*c is greater in the presence of waves because the steadycurrent "feels" a rougher boundary.
5.2.2 Initiation of Sediment Motion
Sediment motion is initiated when the combined wave and current bound-ary shear stress felt by the seafloor is greater than the critical shear stressfor moving sediment. The boundary shear stress TO defines the effects of tur-bulence on the flow in the boundary layer; this stress results from the viscousinteraction of the fluid with the solid boundary and from the turbulence gener--ated due to pressure gradients introduced by roughness elements on the bottom.These two components of the boundary shear stress are referred to as skin fric-
5-6
tion and form drag. The medium sand and smaller grains which are of primaryinterest in suspended sediment transport are not set in motion by the pressuregradients which make up the form drag component. For the purposes of this mod-el, initial sediment motion is considered to result from the skin friction com-ponent, denoted by the symbol r'O' whereas turbulent transport of mass and mo-mentum in the boundary layer is governed by the total boundary shear stress.
A sediment grain responds essentially instantaneously to turbulentfluctuations. Therefore, critical shear stress for initiation of motion mightbe expected to be related to the skin friction component of the maximum bound-ary shear stress rO . In controlled lab settings initiation of motion andcwbedload transport in oscillatory flow were found to be quite successfully pre-dicted using the maximum shear stress (Madsen and Grant, 1976, pp 18-28,40-45). In those cases, the bed was flat, so the maximum shear stress wasequal to the skin friction shear stress. In the model, the skin friction com-ponent of the maximum combined boundary shear stress is used for all initiationof motion and bedload transport predictions.
A commonly used empirical criterion for determining the critical shearstress for initiation of motion of non-cohesive sediments is the Shields para-meter, which is defined:
l/J = (s - l)pgdr ' o (5-9)
The numerator represents the force trying to move the particle and the denomi-nator represents the gravitational force (per unit area) on the particle, whichresists motion (s - p dip, p d - grain density, g - gravity, and d = grainse sediameter). When the critical value of Shields parameter for the grains in thebed is exceeded by the flow, sediment is put into motion. The critical valueis designated l/J •c
Critical values for the Shields parameter have been determined empiri-cally in a series of laboratory experiments, beginning with those used to gen-erate the original Shields Diagram (Shields, 1936). That original diagram
5-7
plotted ~c vs the boundary Reynolds number R*- u*d/v; this was !eformulated byMadsen and Grant (1976) to make the independent variable a function of sedimentand fluid properties only. The modified Shields Diagram plots ~ vs a non-dimensional sediment parameter S* where
dS = --)(s - l)gd* 4v(5-10)
The original flume experiments on which the diagram was based were performedusing only large grain size material, corresponding to grain diameters of medi-um sand or larger (R* > 1 and S* > 1). Later in~estigators did experimentswith grains as d .0016 cm (medium silt) (White, 1970) and extended theShields Diagram from R* - 1.0 to R* - 0.05. These results have been adapted tothe S* formulation; the result is Figure 5-1. This figure shows the initiationof motion criterion which is used in this model. The initiation of motion cri-terion can be increased by biological adhesion of sediment grains (Grant, Boyerand Sanford, 1982) or plastic cohesion, due to the presence of clays in evensmall quantities. This is especially true for silt-sized grains, so interpre-tation of sediment load and transport results must be made with this uncertain-ty in mind.
5.2.3 Sediment Suspension
Once sediments are dislodged from the seabed, they are available fortransport upward by turbulent eddies. As described above, the strength ofthese eddies governs the mixing of mass and momentum in the boundary layer andis determined by the boundary shear stress, TO. Mixing occurs because verticaleddies are transporting high-concentration fluid up and low-concentration fluiddown, so that there is a net upward flux of sediment based on the concentrationgradient. This flux is balanced by the tendency of the sediment to fallout ofsuspension due to gravitational force.
The tendency of the sediment to fall is measured by the particle fallvelocity wf and is determined to first order by balancing the submerged parti-cle weight with the fluid drag on the particle. For grains smaller than fine
5-8
I 11'1 i I I I H-f1---.'--+I-+I-.-.I-i-i-++-t-t --+--+-+-++otT
-,-,
"
10'"~--...-.,.-.---t-- -...-...-l+f'-------ot-+_...,.. __ -+_+_+ __I_++t_10'"
Extended Shields CUfVe
10 .S.-d'/(.-t J.t4I411 10' 10'
Figure 5-1. Modified Shields Diagram, extended to include fine grain data (modified fromMadsen and Grant, 1916)
5-9
[(s _1)gd]1/2(5-11)
sand (diameter of 0.012 cm), Stokes drag law holds and the fall velocity isgiven by:
the particle. The fall velocity of a particle in the field, however, can beaffected by flocculation or biological aggregation.
The distribution of sediment in the water column is governed by theconservation of mass equation for sediment:
ac _ (ac) a <c' "> _ 0at Wf az + az w (5-12)
where C is volumetric sediment concentration and <C' w'> represents then n
Reynolds averaged turbulent fluctuation of sediment. Analogous to the eddyviscosity representation for turbulent stress, turbulent mixing of sedimentcan likewise be modeled using an eddy diffusivity, so that
<c'w'> (5-13)
Experimental evidence indicates that the eddy diffusivity and viscosity havesimilar forms in boundary layer, and v can be written asts
vts (5-14)
where 1 is an empirical parameter, assumed to be 0.74, based on Businger andArya (1974). The GMG model assumes steady state conditions, with a balance be-tween upward turbulent diffusion and fall velocity, thus Equation 5-12 simpli-fies to
ac-wfC + v (--a) - 0ts z (5-15)
5-10
"'(Wf
C(z) - C (~) ~u*cwo zo zo < z < S cw (5-16)
which is satisfied by
"'(WfC zC(z) - S (---) ~u*ccw S cw
z > S cw (5-17)
where Co is a reference sediment concentration, discussed below, and CScw isthe concentration at the top of the wave-current boundary layer, determinedfrom Equation 5-16.
Note that the GMG model assumes zero net vertical flux of sediment,since the fall velocity exactly balances the turbulent flux. This constraintis not valid for application of the GMG model as a boundary condition to atime-dependent transport model, and a slight modification is required to gener-alize the model to conditions of non-zero vertical flux. This is discussed inSection 5.4.
5.2.4 Reference Sediment Concentration
The reference concentration Co is calculated using the form suggestedby Smith and McLean(1977):
"YOSC - C ( ) (5 -18)o bed 1 + "Y So
where Cbed is the bed concentration of the grain. "YO is an empirical reference-3concentration parameter of order 10 . S is the normalized excess skin friction
l' ' - r~S =
0 C
r YJcc
The primes refer to the skin friction component of the total boundary shearstress. The skin friction component is determined by calculating the combined
5-11
The reference concentration is directly dependent on the criticalshear stress, as determined by the Shields parameter. However, the Shields pa-rameter is an empirical value based on laboratory flume experiments on singlegrain-size sands. Mixed grain sizes and biological binding or mixing, as foundin field situations, may affect the critical shear stress.
wave/current friction factor f using the dominant grain size as the bottomcwroughness scale rather than the physical boundary roughness which includes theeffect of ripples and sediment in motion. To handle the presence of waves inthis model, the instantaneous normalized excess shear stress is used to calcu-late instantaneous reference concentrations which are then averaged over a waveperiod to find the mean reference concentration.
5.2.5 Suspended Sediment Stratification Effects
The vertical gradient of suspended sediment results in stable strati-fication in the boundary layer, which causes a partial suppression of turbu-lence and a reduction in the eddy viscosity and diffusivity. The GMG modeluses the form developed by Businger and Arya (1974) for stable stratificationin the atmospheric boundary layer, in which turbulence was related to theMonin-Obukov 1enth, which in the case of suspended sediment can be approximat-ed:
L = --:-----::-:-~-
3lu*1
Itg(s - l)wfC(z) (5-19)
where s is the specific gravity of the suspended sediment and the concentrationrepresents the total concentration for all grain sizes considered.
The sediment concentration profile is coupled with the velocity pro-file through modification of the eddy viscosity and diffusivity to reflect theeffect of stratification on turbulent energy:
/.I =0t (5-20)
5-12
II -ts (5-21)
where P is an empirical stratification parameter, assumed to be 4.7 (Busingerand Arya, 1974). The Monin-Obukov length L becomes smaller as the suspendedsediment stratification increases, which causes a reduction in the viscosityand diffusivity. The dependence of the eddy coefficients on stratificationcauses the vertical profiles of velocity and suspended sediement to vary withincreasing stratification. The solution for velocity and suspended sedimentmust therefore be approached iteratively, with corrected values of II and lit
t scoming from extimates of the concentration distribution C(z).
The solutions for the velocity and suspended sediment profiles, withthe inclusion of the stratification correction are as follows:
u(z) -.!u [In -~ +f .!dz]~ *c zOc 5 L
cwz > 5cw (5-22)
C(z) .:pWf 1exp - {---- -Ldz}
~u*c 5cwz > 5cw (5-23)
The effects of stratification are shown in the second term on the right handside of Equation 5-22 and in the exponential term in Equation 5-23. Becausethe high energy of the eddies in the wave boundary layer is expected to keepthat region well mixed, the stratification correction is not included in thecalculation of the velocity below 5 The velocity and concentration profilescwinside the wave boundary layer are therefore given by the neutral solutions,Equations 5-6 and 5-16.
5.2.6 Bedload and Suspended Sediment Transport
Transport of sediment in the near-bottom layer is calculated by numer-ically integrating the product of the predicted concentration and velocity pro-files:
5-13
q -1C(z)u(z)dzs,sus Zo (5-24)
For sediment larger than medium-coarse silt, most transport is expected to beconfined to the near-bottom layer.
Bedload is not expected to be a significant portion of the total loadin the wave-dominated shelf flows over beds of sand and silt on which thisstudy focuses. It is estimated using a semi-empirical bedload formula as out-lined in the following paragraphs; this estimate is sufficiently accurate forthe purposes of this model. Since the bedload is assumed to travel in the di-rection of the wave-current shear stress, however, and the suspended load di-rection is controlled by the current, the bedload could be a major contributorfor some size classes in the direction of the wave.
The bedload is 'ca1cu1ated using the Meyer-Peter and Muller (1948) for-mulation, an empirical formula based on an extensive set of laboratory experi-ments:
3/2q b d - 8[d/(s -l)gd](~'-~ )s, e c (5-25)
where the Shields parameter is calculated using the skin friction value of theshear stress. We want to apply this equation, which was formulated for steady,unidirectional flow, to the combined wave/current flow. For this, we assume,as we do for the reference concentration calculation, that the response timefor the sediment is small relative to the unsteady time scale (as demonstratedin Madsen and Grant, 1976) and that the maximum shear stress in each directiondominates the boundary shear stress. This estimate will be larger than theactual bedload, but will provide a reasonable scale for comparison with thesuspended load to see if the bedload is significant.
Since we assume that the maximum boundary shear stress in the direc-tion of the current is equal to the sum of the wave shear stress and currentshear stress, we likewise assume that the maximum boundary shear stress in the
5-14
(5-26)
opposite direction (r ) can be calculated by subtracting the current shearcw,negstress from the wave shear stress (r - r - r ). (Codirectionalitycw,neg w,max chas again been assumed for ease of discussion.) If we assume that the maximumshear stress in each direction occurs for 1/2 the wave period, we overestimatethe bedload transport in each direction; however, to 'time average' the trans-port we subtract the value in the negative direction from that in the positivedirection, cancelling most of the error. To calculate total bedload transport,we determine for each grain size class n the following:
where ~' is the Shields parameter in the negative direction, based on r- cw
5.2.7 Bottom Roughness
The calculation of the velocity profile inside the wave boundary layer (Equa-tion 5-6), depends explicitly on the physical bottom roughness length zOo Thislength is also necessary for the calculation of the friction factor f oncwwhich the calculation of the shear velocities depends. Its value is thereforeof fundamental importance.
A model for movable bed roughness under a combined wave and currentflow was developed by Grant and Madsen (1982), and that work will be describedbriefly here. Their model is used in GMG.
The physical roughness felt by the near-bottom flow is the sum of thethree ~omponents: 1) the roughness due to the individual grain diameters inthe bed (skin friction); 2) the roughness due to ripples and mounds on the sea-floor (form drag); and 3) a roughness associated with dissipation due to sedi-ment in motion in the near-bed layer. The effect of these elements will be pa-rameterized in terms of a Nikuradse equivalent sand grain roughness, As usedhere, the roughness height is expressed in terms of the three elements listedabove so that the total roughness height is:
~ = ~,gr + ~,rip + ~,s.t.5-15
5-(27)
where the three terms on the right hand side represent the roughness due tograins, ripples, and sediment transport, respectively.
The grain roughness, k is represented by the grain diameter d. For-o,gra flat bed, the grain roughness is the only roughness element, and the skinfriction is the total roughness. In most continental shelf situations, how-ever, there are either hydrodynamically or biologically generated roughnesselements at least an order of magnitude greater than the grain size, so thatthis element can be neglected. It should be noted, however, that the sandgrain size is the appropriate roughness length for the skin friction componentof the total boundary shear stress, on which initiation of motion and bedloadcalculations depend.
The form drag component of shear stress is generated by the formationof eddies in the wake of the roughness element and the reattachment of the flowbetween elements. The-roughness is dependent on the shape and distribution ofthe elements. Grant and Madsen (1982) derive an expression for roughness asso-ciated with a two-dimensional wave-generated ripple with height equal approxi-mately to its length:
k . = 27.7~(~)-o,r1p A(5-28)
where ~ and>. are ripple height and length.
The dimensions of the ripple are best determined from direct observa-tion of the seafloor in the region in question. When this is impossible, orwhen the roughness is in transition, empirical bedform formulas can be used.The model used in this work, since the cases of interest are wave-dominated, isa model of wave-generated ripples discussed in Grant and Madsen (1982). Forboundary shear stress only slightly greater than that needed to initiate mo-tion, Grant and Madsen found that ripples change only slightly with changingshear stress, in what they refer to as 'equilibrium range'. At higher shearstresses, ripples grow smaller rapidly as they are washed out. The shearstress where this process begins is designated by a breakoff Shields parameter:
5-16
(5-29)where S*criticalships for
is a non-dimensional grain diameter (Equation 5-10) and ~ is thec
Shields parameter for initiation of motion. The empirical re1ation-ripple geometry under waves given by Grant and Madsen are:
!L 0.22(f)-0.16t\ c~c< l/J' < l/JBs. 0.16(f)-0.04
Aand c
!L ~ 0.48S~·8(f)-1.5t\ cl/J' > l/JB
i~0.28S~·6(~)-1c
These values are used in Equation 5-28 to calculate ripple roughness in themodel.
The roughness associated with sediment transport is based on argumentsadvanced by Owen (1964) that the wake structure around sediment grains in thenear-bed transport layer cause the flow to feel a roughness proportional to thethickness of the layer. This concept was applied by Smith and McLean (1977) tosteady flow in the Columbia River and by Grant and Madsen (1982) to oscillatoryflow. Grant and Madsen derive an expression for the layer thickness by balanc-ing the initial kinetic energy of a particle put into motion with the potentialenergy at its highest elevation. The roughness length they derive, using datafrom Carstens, et aI, 1969) is expressed:
kb - 11.1(s + C )dl/J[(~)1/2_ 0.7]2S.t. m c Y'c
where C - 0.5 is the coefficient of added mass of a sphere.m
(5-30)
The roughness length Zo in fully turbulent flows as considered in themodel is equal to ~/30. The expression used for the roughness length is
5-17
therefore given:
The
Zo - ('1riP:r~p)+ 5.3(s + em )d1/lc[(~)1/2- 0.7]2+ ~Or1p
three terms on the right hand side represent, respectively, ripple rough-(zO,rip)' sediment transport roughness (zO,s.t.)' and grain size rough-
(5-31)
nessness.
5.3 RUNNING THE GMGMODEL
The interconnections of these disparate elements, and the generationof the results, might be better understood by using a step-by-step ex~inationof how the boundary layer model works. The computational procedure, asdiscussed in the preceding sections and applied here, is traced in Figure 5-2.Each line in the flow chart is labelled, and those labels are referred to inthis discussion.
There are three inputs (Line 1) to the model at each point: (1) cur-rent velocity (u) at some height within the current boundary layer and above
rthe wave boundary layer, (2) wave climate, consisting of maximum wave bottomvelocity (~) and wave excursion amplitude (~) (or, equivalently, wave height(H) and period (T) and water depth (h», and (3) sediment size (d), density andtexture. (For simplicity, co-directional wave and current and a single grainsize bed are assumed in this discussion.) The example presented is a moderatestorm ~ave, with a 26 em/sec current measured one meter above the bottom, whichis composed of coarse silt. The model input parameters are as follows:
~: 40 emsecH 2.6 meterh 50 meters
26 emur sec
d 0.006 em.
~: 96 em.
T : 15 seconds
z : 1.0 meterr
Ps 2.65 gm3em
5-18
.u.
.' .
1
J.
3"
5-19
(c.,,· •••••ctl•••"'••••.C./~-')
CJaJa/. ft .••a '~}" fC.h( First $')
C4Jc.J-.h ref•. _e. ••.'-'~_lit SlrJil:. trIk .
It s ',.• s"'~/0" iINII 1r~/, __ "",,1,,./
are referred to in text
Flow chart tracing computational procedure Corboundary layer model. LabelsFigure 5-2.
The first step in the model is to make a guess at the current contri-bution to boundary shear stress on the bottom (Line 2a). This is representedas u I~, where u represents the mean velocity at some unspecified heighta 0 awithin the wave boundary layer. The model makes an initial guess that ua/t;, =
ur/t;,.
This shear stress estimate is used with the grain roughness (d) in theequation for the friction factor (found in Section 5.5) to calculate the skinfriction component of the friction factor (f f; Line 2b). That friction. cw,sfactor is necessary to test for initiation of sediment motion. It is used tocalculate the skin friction component of the maximum bottom shear stress TO'
and, from that, the Shields parameter for the flow (Equation 5-9). If theShields parameter is less than the critical value for the sediment on the sea-floor, no sediment moves (Lines 2c - 2e). In that case, the skin frictionshear stress is the same as the total shear stress. If sediment is moving,however, and no bed ~oughness was specified as input, the boundary roughnessdue to ripples and sediment transport is calculated according to Equation 5-31,and that roughness is used in the friction factor equation to calculate the to-tal friction factor f (Line 2f). The total f is used to calculate the meancw cwand maximum shear velocities (see Section 5.5). From these, the first guess atthe predicted reference velocity is calculated using Equations 5-6 and 5-7(Line 2h). If the predicted velocity is not acceptably close to the given ref-erence velocity (as it will certainly not be on the initial try), the modelchooses another value of ua/t;" and proceeds again through the steps just de-scribed. If the predicted value was too low, the value of ua/t;, is multipliedby a factor of 2.05; if too low, the parameter is halved. Iterations continueuntil the predicted and given currents match. At that point,the neutral veloc-ity profile is calculated using Equations 5-6 and 5-7 (Line 2j).
If sediment was put in motion, the sediment concentration profile iscalculated, first without including stratification corrections to either veloc-ity or concentration profiles. The particle fall velocity is determined and thesediment reference concentration is determined from Equation 5-18. These areused in Equations 5-16 and 5-17 (neglecting the exponential term in the latter)to calculate the sediment concentration profile (Line 2n).
5-20
The stratified calculation begins, as does the neutral one, with aguess of ua/~' Initially, the value which produced the neutral case solutionis used. This results in a prediction of reference velocity which is higherthan the given reference velocity, since stratification increases velocitiesabove the wave boundary layer. The same steps as for the neutral case are fol-lowed through calculation of the shear velocities at Line 3f. At this stage,the calculation of the stratification-corrected concentration profile begins.
Finally, the velocity and concentration profiles are integrated to de-termine the neutral load and transport predictions. The estimated bedload iscalculated using Equation 5-26.
The neutral results for the wave case described above are shown in Ta-ble 5-1. Note that the value of u drops by a factor of three from the firstaguess. Most of the roughness is generated by ripples (compare Zo . vs.,r~pZo ), and the additional roughness increases the friction factor signifi-,s. t.cantly (compare f f vs. f ). The wave-current shear velocity is more thancw,s . cwtwice the current shear velocity. The predicted bedload transport is insigni-ficant compared with the suspended transport. The predicted neutral velocityand concentration profiles are shown in Figures 5-3 (a) and (b).
First, the concentration profile without the stratification correctionis calculated, as for the neutral case. That profile is used to determineMonin-Obukov Length (Equation 5-19), which is substituted into Equation 5-23 toget a revised estimate of the concentration profile (lines 3g and 3h). Thisprovides a revised estimate of the integrated Monin-Obukov Length (Lines3i-3j)~ If the difference between the old and new integrated M-O Length valuesis greater than the allowable error, the new value is used to calculate anotherrevised concentration profile. These iterations (Lines 3i-3k) continue untilthe integrated M-O Length values converge.
Once the concentration profile is determined for this ua/~ value, the
5-21
Neutral results for sample run
!!&.203 few ••, 4.745 x 10-3•••
til", 0.5657 tP. 0.1226-Zo 8.837 x 10-2em Zo."" 6.226 x 10-2 em
Zo,C 1.432 em Zo••.,. 2.591 x 10-2emfew 2.907 X 10-2
u.c 2.46 em/sec U.ew 5.802 em/secDew 11.13 em !A.
16.41 mIsusp. load .6294 ::;susp. tran 22.65~a/cn1/&ec bedload .0663cn13/cn1/&ec
Table 5-1. Some resu1u forneutr.,J, near-bottom model run for a moderate storm wave on the
continental shelf, ud-=ribed in text. Load and transport are calculated for near-bottomlayer, d-.ipated z < t
5-22
Near Bottom Wave and Current ModelMod.storm wave,silt 13-apr-.87Neutral Velocity Profile Stratified Velocity Profile
I10·
10J
.....•.•102E
U'-" 10N- 1s:C)
~ 10-1
10-2
10-J
o 25 50 75Velocity U (cm/s)
Neutral C<;).ncentration1o· ---+H-HffI-hHfHlI-1l-++foffll--++++fHIi1r-
10J
E 102
o'-" 10N-.s:C)
~ 10-1
10-2
10 -J -4-~-HfllI.-hI-HNIIo---1I-++1Iffl1--+++Hfflf-
10-5 1a... 1O-J 10-2 10-1
Concentration
a 25 50 75Velocity U (cm/s)
Stratified Concentration
10-5 10-4 10-J 10-2 10-1
Concentration
Figure 5-3. Predicted neutral and stratified velocity and concentration profiles to a height
z = t- for a moderate storm wave with a reference current of 26 em/Me
5-23
new reference velocity prediction including stratification effects can be cal-culated using Equation 5-22. As in the neutral case, if the predicted and giv-en values are outside acceptable error limits, iterations of Lines 3a-3m beginagain with a revised ua/~ value. Once the velocity values converge, the finalstratified velocity and concentration profiles and the transport and load pre-dictions are calculated.
The stratified results for the wave case described above are shown inTable 5-2 and Figures 5-3 (c) and (d). Compare these with the neutral caseresults shown in Table 5-1 and Figure 5-3 (a) and (b). The sharp drop in con-centration and increase in velocity above the wave boundary layer can be seenby comparing the neutral and stratified profiles in Figure 5-3.
The largest changes from the neutral case result from the reduced cur-rent shear velocity: u*c is approximately one-half the neutral value. For thisreason, 0 /6 drops to 9.4 m in the stratified case from 16.4 m, and the sus-
cpended load and transport drop by an order of magnitude or more.
Parameters which reflect only wave boundary layer conditionsmuch less: The wave-current shear velocity u* and wave boundary layercwo are essentially the same; the roughness prediction rises slightlycwstratified case because the ripples are left intact by the smaller currentshear stress; the sediment transport roughness drops somewhat. Bedload trans-port drops by only 25%, but is still insignificant compared with suspended
changeheightin the
transport.
5.4 APPLICATION TO A SUSPENDED PARTICULATE FLUX MODEL
While the GMG model solves for steady-state distribution of velocityand suspended sediment, it can be applied to time-dependent problems if thevertical scale of the boundary layer is small enough that the vertical flux di-vergence terms are much larger than the time-dependence of the currents andsuspended sediments within the boundary layer. This condition is satisfied ifthe GMG model extends over a small fraction of the total boundary layer height,
5-24
Stratified results for sample run
1_,./ 4.861 x 10-1 !II. .0539•••til", 0.4448 .p. 0.1226
Zo 1.317 x 10-1em Zo,ri" 1.135 x 10-1 em
Zo" 3.646 em Zo,• .I. 1.7937 x 10-2em
f_ 3.659 x 10,..2
u•• 1.418cm/sec u._ 5.702 em/sec
6_ 10.95 em fa. 9.45 mIS
susp. load 0.0373 :::
susp. tran 0.7430 cma/cm/~ec bedload .0482cml/cm/~ec
Predicted u,., with ~ = 0.203 : 39.0 em/sec
Table 5-2. Some results for stratified near-bottom model run for a moderate storm wave,
strong current, and a lilt bed 011 the colltinental shelf. Load and transport are calculated
for Ilear-bottom layer, designated z < t-. Predicted velocity 011 bottom line is the rault
for ,the IIfttral C1UNIlt mear It~
5-25
for instance:
z < 0.1r
For practical application, z can be as little as a few meters, thus minimizingr
the errors due to neglecting time-dependence in the boundary layer.
The GMG model can provide an estimate of the bottom stress and thenear-bed suspended load, based on the input of the directional wave data, sedi-ment size and texture in the bed, and the velocity at the matching level. Fromthe standpoint of a circulation model, it can be thought of as a black box mod-el of the effective bottom drag coefficient. However, in order for the modelto be used for prediction of vertical flux of suspended sediment into the do-main of the overlying model, a minor modification must be made of the equationfor suspended sediment distribution.
The modification is made as follows: Rather than assuming that thereis zero vertical flux of sediment, the vertical flux is allowed to vary depend-ing on the concentration at the matching level z between the boundary layer
rmodel and the outer flow model. At that level, the concentration of suspendedsediment is specified, based on conditions in the overlying model, which inturn is subject to the vertical flux condition of the GMG boundary layer model.Considering for simplicity a simple current boundary layer without stratifica-tion, the solution for a steady-state sediment distribution is
where Cl and C2 are constants. When the vertical flux is zero, Cl is zero andthe solution is the same as in GMG. For application to a suspended particulateflux model, Cl is not zero, but rather it is adjusted to satisfy the conditionat the top of the boundary layer.
The bottom boundary condition will remain the same, so that Cz = z00 This gives
5-26
"'(wf
C(z) - Cl+ (Co· Cl)(: )- ~u*co
Satisfying the boundary condition that C - Cr at z - zr' where Cr is specifiedby the overlying model, gives
"'(wf
"'(Wf1 _ (L..). ~u*cZo .
Generalizing the result to the case of a wave-current boundary layer and a cur-rent boundary layer, we have to match the solutions at 6 , obtainingcw
C -1
C -1
C - Coor 0 s r1 - 0 0s r
where
os
and
zror = (-6-)
cw~u*c exp -
~u*cs 1-dz
L6 cw
This solution will have to be iterated several times, since the stratificationcorrection will change, depending on the value of Cl" The Monin-Obukov length Lwill not depend on the total concentration, but only on the z-dependent part,so
L
5-27
The vertical flux of sediment is constant across the boundary layer, and it issimply equal to -C1wf. If C1 is positive, the flux is downward, and if C1 isnegative, the flux is upward.
5.4.1 Interfacing With a Wave Prediction Model
With this modification of the GMG model, the suspended sediment fluxas well as the stress are determined at the top of the boundary layer, based onmatching the velocity and the concentration at z. Suspended sediment of mu1-
rtip1e size classes or a single size class can be considered with equal facili-ty, depending on the needs of the model.
The GMG model requires the orbital velocity and frequency of wave mo-tion near the bottom. This may not be the spectral peak, because shorter waveswill be attenuated with depth according to the short wave particle excursionrelation:
H w2 sinh kh (5-32)
where H = trough-to-crest wave height, k is wave number and h is water depth.It is a straightforward matter to integrate a model-derived wave spectrum todetermine the peak near-bottom oscillatory current as a function of sea state.
5.4.2 Problems
The single most difficult problem with the GMG model is the estimationof near-bottom sediment concentration CO' This quantity has only been arrivedat empirically; there is no theoretical basis for its estimation. The problemis far worse in the case of cohesive sediments than non-cohesive sediments,since the threshold for resuspension is not well known, and resuspension isstrongly dependent on biological processes. For particles finer than sandysilt, the properties of suspended sediment become very difficult to quantify.
Another problem area is the question of stratification-induced stabi1-
5-28
ity. While the concept is well-documented for thermal stratification in atmo-spheric boundary layers, there is still some uncertainty in application tosuspended sediment. The matching zone between the wave-current and currentboundary layers appears to be particularly sensitive to stratification effects,and more research is required to ascertain the proper means of representing thestabilizing influence of stratification.
As a final difficulty, it should be noted that the GMG model is notreadily compatible with the open ocean oil weathering code. Therefore, ele-ments of the GMG model are unlikely to be incorporated into the oil weatheringcode at this time.
5.5 APPENDIX: FRICTION FACTOR, SHEAR STRESS AND SHEAR VELOCITY SOLUTIONS
The characteristic boundary shear stresses and shear velocities arecalculated from the instantaneous boundary shear stress. The instantaneousboundary shear stress is defined in GMG using a quadratic drag law:
122 u2Pfcw(u + v)[ 2 2 1/2(u + v ) (2 2)1/2u + v
v 1 (5-33)
where u, v are the x, y components of a combined wave and current reference ve-locity close to the bottom (though we are, for the moment, assuming that thewave and near-bottom current are collinear in the x-direction). f is thecwcombined wave and current friction factor. The characteristic shear stress inthe wave boundary layer (TO P u2* is defined as the maximum value ofcw cw 2Equation 5-33. For the current boundary layer, TOC (= P u *c) is calculated bytime averaging equation 5-33. The solutions for the shear velocities are:
(5-34)
5-29
(5-35)
where ~ is the angle between the wave and current directions, Q and V2 arefunctions of the maximum and time-averaged velocities, respectively, in thewave-current boundary layer. u is a representation of the velocity of the
amean flow in the wave boundary layer, so ua/~ is a representation of the rela-tive strength of the mean versus the maximum oscillatory flow in the waveboundary layer. The value of f is determined using these definitions and thecwwave velocity profile. The value of f ,is calculated implicitly with thecw .equation:
3/4Q
4 (5-36)
where Q and V2boundary layer,wave, defined:
are functions of the maximum and mean velocities in the waverespectively. ~ is the bottom excursion amplitude for the
(5-37)
and K is derived from the equation for the wave velocity, defined below, and isdefined:
K 1 12r 1/2 (ker22ro1/2 + kei22ro1/2)1/2
0
The solution for the wave momentum equation insidenot explicitly of interest for the present problem,
the wave boundary layer isthough it is necessary for
the calculation of the boundary shear stress. The solution is:
uw
71'lne + 1.154 + £-2~ [1 + e£wt]
o k 2c1/2 k ·2c1/2ner .•O + e~ .•O(5-38)
5-30
where e - xiS and eO - xOIS . Ker and kei are Bessel Functions: tabulated. cw cwsolutions to a particular form of differential equation. The derivation andbackground for the wave velocity profile and friction factor equation are cov-ered in some detail in Grant and Madsen, 1979.
5-31
6.0 EXECUTIVE SUMMARY
The objective of this study was to characterize the nature of oil/sus-pended particulate material (SPM) interactions such that predictive mathemati-cal formulations could be derived and (ultimately) incorporated into an open-ocean oil spill trajectory and circulation model. Dispersed oil drop1et/suspended particulate material (SPM) interactions provide a potential mechanismfor transport of spilled oil to benthic marine environments. Section 1 of thisreport contains a detailed review of previous field and laboratory studies andour knowledge of the mechanisms involved (including uncertainties on oil drop-let dispersion, turbulence requirements, sediment flux, and oi1/SPM interactionkinetics).
Oil and SPM interactions occur through two primary mechanisms: 1) oildroplets colliding with suspended particulate material and 2) molecular sorp-tion of dissolved species. Chromatographic profiles presented in Section 1(Figure 1-1) l11ustrate the selective partitioning of intermediate and highermolecular weight aliphatic (Fig. 1-lA) and polynuclear aromatic (Fig. 1-10) hy-drocarbons onto suspended particulate material. The chromatograms also demon-strate the concomitant selective lower molecular weight (one ring) aromatic hy-drocarbon dissolution (Fig. 1-lG) into the water column.
The parameters and/or conditions that might influence the rate of "re-action" between dispersed oil droplets and SPM are numerous and include: con-centrations of dispersed oil and SPM, size distributions of the oil dropletsand SPM, composition of the oil and SPM, the extent of previous weathering anddissolution of individual components from the dispersed oil droplets, and theturbulence required for mixing. Data from field and laboratory studies suggestthat SPM sorption of truly dissolved components is not important to the overallmass balance of oil from a spill; however, such adsorption may be important forbiological considerations.
As initially envisioned, this program was initiated to examine therate of oi1/SPM interactions for the purpose of developing a mathematical modelto predict the potential for sedimentation of components of spilled crude oil
6-1
An appropriate three dimensional mass balance equation for the concen-tration of a given species i yields the following partial differential.
and refined petroleum products. The development of a model for this interac-tion was intended as an "add on" calculation (or sub-routine) to a general cir-culation model that addresses both vertical and horizontal transport. All cir-culation models are essentially solutions to momentum transport equations, andsediment transport depends on ocean circulation for modeling purposes.
aCi a a aa + --a(V Ci) + --a(V C.) + --a(V c.)t x x Y Y ~ z z ~
(6-1)a aCi a aCi a aCi--(k -) + --(k -) + --(k -) + Rax xax ay yay a zaz iz
This equation allows for calculation of a mass balance that yields theconcentration of species i when integrated over time and space. This equationappears in numerous branches of science and engineering when mass balance con-siderations are encountered. In the equation, the left-hand side, with the ex-ception of aC./at, represents advection through a differential volume element~that is fixed in space. The right-hand side, with the exception of R., de-i.
scribes horizontal and vertical dispersion. This partial differential equationis the basis for discussing and describing oil and suspended particulate mate-rial interactions in the water column. All of the "interaction" information iscontained in the reaction term R .. This reaction term can be either a removal~(output) or source (input) term for the species i. Thus, for oi1/SPM interac-tions, it is necessary to describe what species are going to be identified andkept track of. It is not possible to quantify every single species in the sys-tem; there are simply too many. Instead, experience seems to indicate thatsimplifying assumptions can be made.
When these equations are applied with specific boundary conditions(e.g., bottom topography, shoreline, and weather), a specific 3-D circulation
6-2
model is obtained. These models are "huge" because the large number of equa-tions and the form of the boundary conditions make it impossible to "simplify"the mathematics. In essence, every differential element of the model affectsevery other differential element. Integrating an existing circulation modelwith the inputs of oil at the air-sea interface and sediment from the bottomand shoreline (including rivers) will yield a description of oil and SPM trans-port and the interaction of these two additional "species". These species willnot affect general circulation in any way because their presence does not sig-nificantly affect momentum transport. Thus, the fate of oil and SPM depends oncirculation (and weather), but circulation does not depend on oil and SPM. Thedefining equations for oil and SPM are thus decoup1ed and essentially "ridealong" as the momentum equations are solved.
The reaction for oil droplets in the water column describes the rateof collision and sticking of an oil droplet with a suspended particulate (i.e.,a loss of a "free" oil droplet) and the settling (or rising) of an oil droplet.The reaction term R. for"oil droplets can then be described byi.
Rop K C Cop op p (6-2)
where K C C is the rate of collision and sticking of an oil droplet and aop op psuspended particulate to produce an oil-particulate agglomerate. The effect ofbuoyancy of oil droplets or oi1-SPM agglomerates appears in the verticalvelocity term in equation 6-1.
Details of the complete derivation of the mathematics required to gen-erate the rate equation for oil drop1et/SPM interactions are presented inSections 1.2 and 1.3. From these derivations the collision frequency fordilute suspensions of particle (SPM and oil) interactions can be expressed as
. € 1/2 3R = 1. 3 (- ) (r .+r .) n , n .II i. J i. J (6-3)
when R is the collision frequency, € is the energy dissipation(of fluid) per unit time (cm2/sec3), II is the kinematic viscosityis the radius of particles i present at a number density of n.,~
per unit mass2(cm /sec), r.~
and likewise
6-3
for particles j. This equation describes only the collision frequency. Noth-ing is implied about the "sticking" of particles. Essentially, the interac-tions are modeled on a particle/particle basis where number densities for bothspecies (discrete oil droplets and suspended particulates) are required. Thatis, the "concentrations" or number densities of the two reactants are relatedto the rate of interaction (collision and sticking) as described in equation6-3.
Clearly, the above equation cannot be applied directly to oil dropletsand (or) SPM. The obvious problem is that a distribution of particle sizes ex-ists in any real situation, and the above equation is written for a specificsize class only. Therefore, in order to apply the equation to the measured ki-netics of oil/SPM interactions it is necessary to assume that oil droplets in anarrow size range will behave as a mono-sized population, and that SPM in anarrow size range will likewise behave as a mono-sized population. The ratio-nale for these assumptions and their impact on the mathematics of model devel-opment are considered in detail in Section 2. If these assumptions are valid,then the rate equation can be rewritten as
e 1/2R ~ 1.3 (-) kn.n.II i. J (6-4)
where k now "lumps" the unknown information about the particle sizes.
Experimental application of the oil/SPM kinetic equation can be car-ried out in any vessel or flow situation where the independant variables can becontrolled. The experimental methods found to work satisfactorily in this pro-gram utilized well stirred vessels (with no inflow or outflow) with a knownpower input through a propeller. By introducing oil droplets of a narrow sizerange and SPM of a narrow size range into the stirred vessel and measuring thefree oil droplet counts versus time, it was possible to generate rate constantdata for the oil/SPM interaction. Under the experimental conditions chosen tocomply with the modeling (mathematical) requirements, the concentration of SPM
6-4
d Co -k Co (6-5)
remained constant (i.e., its number density did not change). Thus, the rate ofchange of free oil droplets, C , could be defined aso
dt1/2where k - 1.3 (e/v) k Ca p
Integration of equation 6-5 yields
CIn - -kt (6-6)
where CO is the initial oil droplet concentration at time - O. The experimen-otal data, which are the free oil droplet counts normalized to the initialcount, should fallon a straight line on a semi-log plot versus time if the as-sumptions are correct.
Sections 2.2 through 2.4 contain results and discussions of experimen-tal data on the interaction of fresh and weathered Prudhoe Bay crude oil withrepresentative SPM types. Figure 6-1 is representative of the linear regres-sion analysis of free oil droplet disappearance for the interaction of freshPrudhoe Bay crude oil and Grewingk Glacier till. These data were derived fromphotomicroscopic analysis (i.e., counting) of declines in free oil droplet num-bers over time (e.g., see Figure 6-2). Concomitantly, the formation of multi-ple oil/SPM agglomerates and their settling due to density increases could bedocumented as a function of time (e.g., see oil-SPM agglomerates in the photo-graph in Figure 6-3). Using photomicroscopy to obtain rate data on the forma-tion of oil/SPM agglomerates is a much more difficult task (compared to moni-toring disappearance of free oil droplets) because of depth of field focusingproblems with the microscope and the complex distributions of SPM and discreteoil droplets within the oil/SPM floes or agglomerates.
Much more detailed experimental results with fresh and weathered Prud-hoe Bay crude oil and a representative suspended particulate material are pre-sented in sections 2.2 and 2.4. For these more extensive experiments, the
6-5
In(OIL DROPLET-NUMBER) vs. TIME.30 July 1987---Experiment A
fresh Prudhoe Bay crude oil + Grewingk till
(a)5.2
.--. 5.0-0
~ 4.8CIJ 0a. 4.60uCIl 4.40...
'u'E 4.2<,... 4.0CIJ-'lE 3.8:lcCIJ 3.6a.0 3.4...
-0.••....•.c 3.2
3.00 2
y :: 4.54 - (O:0833)x
r2:: 0.91o
4 6 8 10 12 14 16 18 20minutes post -spill
In(OIL DROPLET NUMBER) vs. TIME29 July 1987---Experiment B
fresh Prudhoe Bay crude oil ONLY
y :: 4.70 + (0.00582)x
r2:: 0.18
8 10 12 14 16 18
minutes post-spill
Figure 6-1. Plots of In(oil droplet number density) vs time for experiments withfresh Prudhoe Bay crude oil and Grewingk Glacier till. The
3energy
dissipation rate constant «() was approximately 260 ergs/cm se. ir.each experiment. (a) oil plus glacial till. (b) oil only.
6-6
_ .._------
'l ~" 9.,
r ~ ~.t·, .:. " '.
~\ <,) (1 (.1
e () «" 1(,. '.. ~I
fl'r. • t(;t."C' l\. ". "0
.;cA'I~ 0 <... ~ .. • ?,r ~ ~•.. .,
.t,-Iff ') 14
¢.
" (> <:I. i"-e- \' ,t ...1'''0 ,
" '6»$' ~ii,
~) '" \." ()'~!(r. t .,.I '"
~'i
~..,~ ~
"~4 -~
\: ~..~ ~.~ r. "'. .i.••
.0(j
I';rV", "\. 0 ,:0 •0
.~
" ~• ".• .,1'<. .~" ..., ,~, o~•• ~ !> ~ pP
~.0"
~.• , ~0
~..J. ~
",/'P' .' Q' 0"· .
li "i.
't<
t67f , e,~ .~~~a
,.!• .: It.. •04 ~ .:oc~ c- 'W, -1:0 ".,., . t? q
(1<'. .~. \\,
\0 ....•. ~\a,
•• ,.•.~
JI'.. ~\. ..~
II ('
~ "~ •
At •..~ •~• •...
• ;,~ "{' .~'ttl P
~\, •, \. .....•..,i •. 1:
". ,..
Figure 6-3. Photomicrograph of oil droplet~Grewingk Glacial till SPM agglomerateson the microscope slide at 5 minutes into a stirred vessel experiment.Energy dissipation rate and size scale are as in Fig. 6-2.
6-8
o
o
Figure 6-2. Photomicrograph of blended oil droplets on2 minutes into a stirred vessel exper.~mentrate CE) of approximately 260 ergs/cm sec.50 microns = I I
the microscope slide at~vith an energy dLs sLp ai. iou
Size scale for
6-7
suspended particulate material was selected to represent observed grain sizedistributions (1 to 53 ~m) and relatively high total organic carbon (TOC) bur-dens characteristic of Alaskan Outer Continental Shelf (OCS) waters (Baker,1983). Because of the difficulty in collecting large (kg) quantities of "natu-ral" SPM in the open ocean, ~ 53 ~m sieved-fractions of selected intertidalsediments from lower Cook Inlet were used for most of the studies. The "SPM"so obtained was characterized by X-ray diffraction (for mineralogy), totalor-ganic carbon (TOC) loading, grain size distributions and background compound-specific organic composition by flame ionization detector gas chromatography(FID-GC). These SPM characterizations are presented in Tables 1-2A and 1-2B inSection 1.1.
Rates of oil/SPM interactions under carefully controlled conditions ofturbulence were obtained for fresh Prudhoe Bay crude oil and SPM derived fromJakolof Bay using two completely independent analytical techniques. Both therate of disappearance of "free" oil droplets (as measured by light microscopy;see Section 2.2) and the"formation of oil-SPM agglomerates (quantified by phys-ical separation, solvent extraction and FID-GC; see Section 2.4) yielded oil/SPM interaction rate constants that agreed reasonably well (k = 0.67 x 10-7 to1.8 x 10-7 l/mg) with the different experimental approaches. For these experi-ments the turbulence (as measured by the energy dissipation rate) was approxi-
3mately 260 ergs/cm sec.
Section 3 contains the results of detailed chemical compositionalanalyses of dispersed oil droplets, dissolved components, oiled SPM and sedi-mented oil/SPM agglomerates. Quite clearly, selected oil weathering patternsdue to evaporation, dissolution and compound specific adsorption are observed.The FID-GC data that are presented can ultimately be used to compare computer-predicted oil weathering behavior from the Open Ocean Oil Weathering Code(Payne, et al., 1984) with observed oil-weathering behavior from the stirredchamber experiments. The chromatograms and reduced data illustrate that the1-10 ~m sized oil droplets used in the experiments undergo very rapidevaporation/dissolution weathering (even during the blending/oil droplet gener-ation process). Substantial losses were observed for all components in boilingpoint ranges of 1070 to 3930 F (distillate cuts 1 through 11 as described by
6-9
Payne et a1., 1984). Those compounds remaining (after droplet generation) alsoshowed selective partitioning behavior, and enrichment or enhancement of bothintermediate and higher molecular weight aliphatics and aromatics was observedin the sedimented particle agglomerates as opposed to residual (less than 1 ~m)suspended phases remaining in the water column following the cessation of stir-ring (i.e., turbulence) in the experimental system (i.e., settling column stud-ies). Interestingly, little or no enhancement in settling"velocities of theoil-SPM agglomerates was noted using fresh Prudhoe Bay crude oil and JakolofBay-SPM under the conditions examined. Additional work is currently under wayto further investigate sedimentation rates at varying oi1/SPM ratios with dif-ferent oil and SPM types.
Section 4 contains a discussion of the potential computer requirements(and limitations) for modeling oi1/SPM interactions within the context of afull three-dimensional open-ocean circulation model. As discussed, there areseveral possible approaches including finite element circulation models basedon conservation of mass and energy as well as probability distribution func-tions (PDFs) that might be used to approximate the problem. Finally, Section 5presents an overview of the late Dr. William Grant's contribution to modelingof the bottom boundary layer and sediment resuspension/transport as controlledby non-linear wave and current interactions.
It is significant that several important program elements (e.g. waveand current induced sediment resuspension and transport, breaking wave inducedoil droplet dispersion, and turbulent energy dissipation rate predictions forthe open ocean) are all areas of on going Ph.D.-level research at major univer-sities, oceanographic institutions and private laboratories. As a result,there are still many gaps in our knowledge, and at this time it appears to bepremature to believe that a fully operational three-dimensional ocean circula-tion model that incorporates all of the desired interaction terms (e.g., oildroplet dispersion, sediment resuspension for all size classes of sediment,oil/SPM collisions as a function of oil and SPM loadings and turbulence, etc.)is possible in the very near future. In any case, extensive computer capabili-ties and resources may be required to ultimately develop predictive models thatincorporate all of the variables and stochastic processes involved.
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Therefore, a more pragmatic approach may be the development of a one-dimensional model that would be more useful in providing information which to afirst approximation could be used to assess the potential impact of a hypothet-ical oil spill in SPM-rich waters. In the conceptualization and development ofsuch a model, one must eventually ask, "What will this model ultimately be usedfor, and by whom? How can an environmental studies manager use the results ofthis study and the model to assess and predict environmental damage and re-sponse to a near-shore oil spill? In other words, what is the logical endproduct for this research?"
In the course of answering these questions, it has become apparentthat it may not be appropiate (or even possible) to directly couple the oil/SPMinteraction model with a fully developed three-dimensional circulation model.Instead, as research and model development progressed, the need for astand-alone one-dimensional code that could run on a Personal Computer becamemore apparent. If such a stand alone program were to be developed, what shouldit contain?
o anticipated sea stateo oil type and time from initiation of spillo weather conditionso anticipated suspended particulate loads and types
Ideally, the model should be not only very user friendly but also ca-pable of accepting user input that includes at least the following:
The model would then request a wind speed to which (to the best of ourability and what is currently attainable through the open literature) near-surface energy dissipation rates might be assigned or correlated. Ideally, itwould be nice to estimate the relation between wind- induced sea-surface turbu-lence (potentially represented by Beaufort Sea Scales for which the user hassome intuitive feel) and near surface and mid-depth energy dissipation rates.Then, based on the user specified sea-state, an energy dissipation rate couldbe selected from available published data (representative values are presented
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in section 1.2.1). This energy dissipation rate would then be matched to mea-sured oil/SPM interaction rate constants from the current (i.e., Section 2) andongoing laboratory studies.
An accounting of the dispersion of discrete oil droplets from a sur-face oil slick (i.e., by droplet size, number density, interfacial surface ten-sion, specific gravity, etc.) has yet to be successfully accomplished. This isstill an area of active research being pursued by other investigators. As aninitial starting point, however, a dispersed oil flux into a water column mustbe assumed (or assigned) to provide material for SPM interactions. This topicis currently being investigated by Delft under contract to MMS.
For the purposes of an oil-SPM interaction model, potentially impor-tant user-defined properties of SPM that would be desirable may include:
o total organic carbon (TOC) contento microscopic size fractionationo mineralogical compositiono general surface morphologyo electron microscopic characterization of the <53 ~m size fraction
(Payne et al., 1984).
In designing a mathematical model and experiments to provide data forits verification and implementation, it quickly becomes apparent that there aremore variables to consider than can be reasonably accounted for. For example,Section 2 deals just with the mathematics necessary to generate rate constantsfor the interaction of single sized oil droplets and one size of SPM particles.Obviously, simplifying assumptions are required to model a mixture of varyingoil droplet and SPM sizes. There are also inherent experimental difficultiesin trying to complete measurements of oil and suspended particulate materialinteractions. For example, should only one size of oil droplets be examined?How are the oil droplets to be generated, and can that process be related toenvironmental conditions? Furthermore, can the interaction rate constants becorrelated with open ocean conditions (which are also the subject of intenseongoing research) to develop adequate descriptive mathematical models.
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In summary, model development to adequately describe and predict oil-SPM interaction phenomena and their relation to contributing environmentalvariables is a complex undertaking from both conceptual and experimental stand-points. While all of the difficulties entailed in such an effort have not beenresolved, it is felt that the results of the present program provide much use-ful information and a good foundation toward further model development. As asimpler and more realistic point of departure, an experimenta1y verifiable one-dimensional model (with certain simplifying assumptions) now appears to beachievable. Further laboratory and modeling efforts are being directed at itsdevelopment and implementation in a PC-based form which will have more immedi-ate uti1i1y for environmental studies management needs.
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7-11
APPENDIX A
COMPOUND SPECIFIC HYDROCARBON CONCENTRATIONSFROM 28 LITER STIRRED CHAMBER EXPERIMENTS
fl.I)-('£ lfydmcat"t:JoM with Retent,ton T1~s Greater Than or F..qual to n-CIO
ItItUltUltUUU,ltuu:uuu ••••••••""u ••••••••••••••••••uu"" ••••"•••••••••"uu.J ."" •••••UUc"uJtuu ••••••,tIIu•••••uu" ••••••••••••••••••u ••••u ••••, ••••••••••"''''u ••••••••••••It•••••••••••••••••••••••••••••"ltltu:.'''ftu.. U.UUU ••" ••••••UU ••U ••U •••••••••••••U •••••"UU ••••••••••UU"U ••••••••""'UU"" •••••••••••••••••••••••••••UAftAAItAUftU "'u"' ••••"'••••
Fres h PtulhJe !lay Crude Oil •••• Jakolof !lay SedlI1l!nt8
Tlne aJriaoe 011---- ll!Bpened PI•••• Sl'K__...t __
frna Hydrocarbon OJnoentratlO11B Hydrocarbon QlnoentraU""" Hydrocarbon OJnoentnltlO11B Sl'K lmd Hydrocarbon ConoentraUmo Hydnx:arbon Qn:s.start (ug/g of aU) (ug/1tter sea teter) (ug/!lter sea teter) (. dry (ug/g dry wo1g!1t) (ug/llter)(hra) WltTot.Res. \Of Tot.Res. Tot ••••.••u, WltTot .Res. \Of Tot.Res. Tot ••••.••llt. WltTot.Res. \Of Tot.Res. Tot •••..••llt. wt./l) WltTot.Res. \Of Tot .1Ies. Tot.n-ellt. IDI>Tot.Res. \Of Tot.Res.
0:00- 232211.5 187838.0 443n.5 '1l'/l76.9 0.0 0.0 0.0 0.0 2.0 0.0 2.0 0.4 52.9 38.2 0.0 38.2 7.1 0.0 0.0 0.00.25 37.4 0.0 37.4 32.4 0.0 0.0 0.0 0.0 50.1 : 0.0 0.0 0.0 0.0 25.6 0.0 25.60.50 flJ7.0 528.8 18.2 65.0 61.5 52.4 9.1 5.2 53.0 t1f1J.7 989.2 171.5 '18.2 67.2 0.0 67.21.00 571.2 500.9 10.3 49.1 NIl NIl NIl NIl 47.7 NIl NIl NIl NIl 169.4 0.0 169.42.00 1341.2 1118.0 223.2 157.4 55.7 47.1 8.6 5.1 5103 1lll5.3 917.7 167.6 99.5 552.0 144.6 6tJ7.44.00 2763.1 2275.1 488.0 JJ5.5 45.2 38.9 6.3 4.5 50.1 'lIl1.4 776.4 125.0 89.7 664.0 0.0 664.08.00 4429.0 3710.8 718.2 494.6 1n.8 145.2 28.6 16.9 53.8 3229.6 2698.7 5:11.9 314.4 1107.9 334.5 I3n.4
12.00 8)18.7 6748.5 1210.2 813.3 348.8 290.0 58.8 34.2 48.2 7236.0 flJ16.0 1m.0 110.2 1364.4 2n.9 11JlJO.518.00 1489.4 0.0 1489.4 116tJ.7 539.5 4fIJ.7 18.8 63.6 44.4 12150.7 10377.0 1773.7 1433.2 1365.3 moO IOn.324.00 17350.8 14684.3 2666.5 1382.7 929.1 739.4 189.7 126.7 50.4 18435.3 14671.6 3763.7 2513.1 - 299.3 NIl48.00 34598.8 25973.2 8625.6 5347.4 1974.9 1597.9 377.0 217.] 43.8 45089.7 36481.3 ~.4 4961.0 - 518.9 NIl72.00 292:1l9.6 244567.0 47742.6 31615.0 54444.5 43819.2 10625.3 5898.2 ftJ32.9 3328.7 704.2 398.8 35.9 112336.5 92721.5 19615.0 11110.0 1362.9 726.9 636.096.00 33198.0 25615.9 7582.1 4354.4 1:111.4 876.9 424.6 272.5 28.7 45344.9 JJ55O.5 14794.4 9494.8 1217.6 612.5 605.1
120.00 38406.5 _.5 10317.0 5286.2 997.5 559.3 4:18.2 287.0-- 25.0 39'lOO.0 22372.0 17528.0 1148).0 1500.7 957.9 542.8168.00 52203.9 28704.3 23499.6 15242.4 15m4.7 121453.0 36321.7 21778.1 1475.3 1039.5 435.8 287.4 29.5 50010.2 352]7.3 14772.9 9742.4 1105.2 1225.8 479.4216.00 129510.9 105011.0 24499.9 15994.4 51518.9 41491.1 10027.8 6390.4 12!llI.7 775.4 513.3 338.5 23.0 5fIJ:Il.4 33713.0 22317.4 14117.4 20]5.6 1633.8 6tJ1.8
••••U ••""A•• "••••••••Aft""AAAAA"AA.".AUU•••••A"U •••••"•••••A"A••••••A•••A•••••••••••••••••"" ••uuu •••••••••u •••••••••••UAU ••••••••uu ••u ••••"••"••AUAU ••••••••"u •••••••"" •••".u •••••••""""A •••••••AU•••••U •••••••••ft••••••U •• *"A••ft••••uA •••••AA.uUU*"AAU".""".U.Af:ft**"""UU**A ••••A.U**U •• A.UUU'utAU
2 OIly \leathered PtulhJe Boy Crude OU ft Jakolof Boy 5ed1lIl!nta
Tlne aJriaoe 011---- ll!Bpened PI•••• Sl'K 1'1••••m-l...t __
frna Hydrocarbon OJnoentratlO11B l!ydrocarbon OJnoentraUOI1B Hydrocarbon OJnoentratlO11B Sl'K Iaod Hydnx:arbon ConcentratlO11B IIydrocarbon Qn:s.start (ug/g of au) (ug/!1ter sea teter) (ug/!lter sea teter) ("ll dry (ug/g dry wo1/1lt) ("l/llter)(hra) WltTot .Res. \Of Tot.lIes. Tot •••..••llt. IDI>Tot .1Ies. 1DI Tot.Res. Tot •••..••llt. WltTot.IIes. \Of Tot.lIes. Tot •••..••llt. wt./l) IDI>Tot.IIes. \Of Tot.IIes. Tot •••..••llt. IDI>Tot .1Ies. \Of lbt.lles.
0:00- !UJ34.3 54659.6 25374.7 12132.0 3.3 0.0 3.3 0.0 18.9 14.0 4.9 2.5 51.6 366.3 210.5 95.7 49.2 NIl NIl NIl0.25 NIl NIl NIl NIl 42.5 34.8 7.7 4.8 49.3 861.5 105.1 156.4 97.0 -NIl NIl NIl0.50 973.1 815.5 157.6 107.0 17.0 14.4 2.6 2.0 46.4 367.0 310.8 56.3 42.5 6tJ.5 0.0 40.51.00 1027.0 842.3 184.7 120.0 41.1 33.5 7.7 5.5 46.8 879.1 715.6 163,5 116.9 126.1 0.0 126.12.00 2202.7 1822.9 379.8 213.3 72.4 59.8 12.6 6.6 43.0 1684.0 1391.2 292.8 153.0 NIl NIl NIl4.00 3258).8 26568.6 flJ12.2 3559.8 197.1 164.2 32.9 22.7 34.1 578).1 4815.2 964.8 666.2 123.5 0.0 123.58.50 96012.5 75667.0 20345.5 11595.8 262.9 221.1 41.8 33.5 41.0 6412.2 5392.7 1019.5 816.5 449.2 203.4 245.8
12.00 144588.0 119426.0 25162.0 14383.8 403.0 337.4 65.6 49.6 20.2 19950.5 16103.0 3247.5 2454.8 458.4 133.1 325.315.25 184452.7 147484.0 36968.7 22587.8 434.2 337.4 96.8 55.5 26.4 16447.0 1278l.3 3666.7 2103.8 581.9 325.4 256.524.00 105936.7 86856.1 1'lIl8O.6 10631.1 1464.3 1162.7 :111.6 166.7 25.0 58572.0 46508.0 12064.0 6666.1 58).7 271.8 »1.948.00 86464.7 70336.7 16128.0 'llI)l.5 102.0 82.6 19.4 11.2 3.6 28325.0 22944.4 5]8).6 3115.5 640.9 330.6 310.373.50 78402.6 58111.7 20290.9 1I0f1J.8 62759.8 49718.2 1:1)41.6 6458.5 iso.s 113.5 37.0 n.s 3.8 39597.4 29868.4 9728.9 3639.1 628.3 335.9 292.4
Bot.Sed. 247373.8 202545.0 4482ll.8 249:11.1(n.5 hr)
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start (ug/g of all) (ug/!tter sea teter) (ug/!Iter sea teter) (III! dry (uslg dry •••1g1lt) (ug/!tter)
(hn) WltTot._. \Of Tot .Res. Tot •••..••n, WltTot.Res. \Of Tot.lles. Tot •••..••Ik, WltTot._. \Of Tot._. Tot ••••.••Ik, wt.1l> WltTot.lIes. \Of Tot.Iles. Tot •••..••u. IDI>Tot.Iles. IOl lbt.lles.
0:00- 114082.1 91197.9 22884.2 13432.4 225.9 195.4 :11.5 23.2 SO.8 44.4 6.5 4.6 48.0 1058.8 924.0 134.8 96.5 60.2 44.8 15.4
0.25 1015.6 5627.7 1387.9 833.4 27.1 19.0 8.1 4.9 43.9 616.2 432.3 183.8 112.3 112.2 51.5 :11.7
0.50 27352.0 21522.2 5829.8 3432.9 38.0 29.4 8.6 4.3 48.8 718.5 fIJ2.7 175.8 88.7 75.8 23.6 52.2
1.00 18654.2 14631.9 4022.3 2533.8 34.6 25.9 8.7 5.5 46.4 745.0 558.0 187.1 117.5 153.3 66.6 86.7
2.00 57322.7 41277.5 IfIJ45.2 10061.8 51.5 34.9 16.6 9.6 46.4 1109.5 752.6 356.9 207.0 188.7 71.8 116.9
4.00 711602.9 flJ147.2 18455.7 11423.7 IM.5 134.8 31.7 16.3 45.5 3659.3 2962.6 696.7 358.9 290.6 167.6 123.0
8.00 Il1l237.6 78410.9 29826.7 18491.8 96.7 72.6 24.1 14.7 37.2 2598.4 19~1.6 646.8 393.8 559.4 401.6 157.8
12.00 140206.8 106929.0 33277 .8 21281.4 NIl NIl NA NIl 26.5 NIl NIl NIl NIl 245.8 203.4 42.4
18.00 452846.3 388693.0 64153.3 20710.2 123.5 92.4 31.1 19.5 27.2 4540.0 3398.1 1141.9 717.6 333.9 288.9 45.0
36.00 87688.0 63252.1 24435.9 11033.0 f,{}.4 47.1 13.2 8.0 11.2 5391.1 4208.9 1182.1 712.9 453.7 357.8 95.9
48.00 136798.8 105588.0 31210.8 20457.9 547.3 454.6 92.7 -65.1 21.9 24990.9 20758.0 4232.9 2974.3 3IIl.4 28).6 99.8
72.00 43177 .5 21025.7 221~1.8 1~36R.2 134.1 105.5 211.6 14.1. 6.8 19720.6 15514.7 4205.9 2106.5 554.6 1044.5 110.1
96.00 83399.9 66896.2 16503.7 10123.7 31290.2 0.0 312'l1l.2 23495.9 98.3 76.9 21.4 11.- ~.4 18207.4 14240.7 3966.7 2033.0 610.4 0).1 1111.3
Bot.Sed. 6403.8 5380.8 1023.0 672.6(96.0 hr I
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TlIlI! 9.rrfaoe 011 Surlaoe OIlf •.•• FIlHX; I\m: Hydrocarbon QlncentratiOllB Hydrocarbon Ca1c:entratiOllBstart VIsual (UIl!g of, total oil) (~g of total oU)(hra) Place TIm! AtkJ'tlx nCIO nCl1 nCI2 nCn nCI4 nCI5 nCI6 nCI7 prlata1e nCI8 phytane nCI9 nC20 nC21 nC22 nC23 nC24 nC25 nC26 nC27 nC28 nC29 nC30 nCll nCl2
0:00- KB brIIS en.en 2969.6 2914.0 2976.5 29l)l.2 2324.0 2033.7 1990.1 1601l.1 NA ID7.5 403.6 1162.6 983.6 972.3 953.1 706.5 792.4 624.9 607.3 548.2 337.9 256.6 Tr Tr Tr0.25O.SO1.002.004.008.00
12.0018.0024.0048.0072.00 KB Jm-8S ct4 2598.7 2813.8 D28.0 2911.1 2465.8 2210.6 2470.7 1772.8 NA 1373.8 sn,o 1234.4 1125.2 1161.9 1189.6 910.7 1026.8 ll3J.0 823.7 m.4 448.7 456.2 Tr Tr Tr96.00
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2 IllIy _hered _ Bay Crude 011 lh:I Jakolof Bay --. 2 bIY _l1ld I'tulhJe Bay Crude OIl lh:I Jakolof Bay _
TIllIe 9.rrf ece OIl Surl""", 011f •.•• FIlHX; I\m: Hydrocarbon QlncentrattOlll Hydrocarbon ConoI!ntrattOlllstart VIsual (UIl!g of total oU) (~g of total of!)(hm) Place TIllIe AtkJ'tlx nClO nClI nCI2 nCl3 nCI4 nCI5 nCI6 nCI7 prtst8ne nCI8 phytane nCl9 nC20 nC21 nC22 nC23 nC24 nC25 nC26 nC27 nC28 nC29 nC30 nCll nCl2
0:00- W .lloHl6 CIl-<:14 811.5 1022.6 1047.0 971.5 1041.5 947.0 843.5 794.3 499.3 642.2 275.4 m.1 470.5 461.4 469.5 413.5 388.4 322.1 278.5 182.9 121.7 118.7 93.1 87.3 12.20.25O.SO1.002.004.00 ,8.SO
12.0015.2524.0048.0073.SO U .lloHl6Cll-<:13 678.4 929.7 1021.5 953.3 975.2 924.3 lIl2.6 760.g 483.5 651.3 281.2 560.0 455.6 415.0 400.3 337.0 310.0 248.6 222.2 132.6 92.9 70.5 47.9 42.1 29.2
•••.••.•••• uAU .•.U •.•.••UA a••••.•..•.••uua .••..•..••.H•.•••••.•••.UU •.•••••.•••.• ,UU ••.••U •.•.••.UU •.•UAU•.••.U:UU••.UilAu....•.•.Auauu; ••.•.•.•.•.••.••., "."u" ••.••.•.•.•.•..•.••••.•••.•.•UUUU.UM •.••.•AIU•.••••••••••.•.•.•.•• au •• tAiM•••••••••• _••••••••• U•.••.••••.•.•.••.••.•.••. ..•..............•..12 IllIy Weathered Pndloe Bay Crude Oil and Jakolof liliy ~t8 12 IllIy Weat~ I'tulhJe Bay Crude Oil and Jakolof liliy Se<II.-ta
TIlE 9.rrfaoe 011 9.rrf see 01 t,f""" FIlHX; I\m: Hydrocarbon Qlncentl'llUOIlB Hydrocarbon Ib1centratlOlllsUrt VIsual (ug/g of total ott) (ug/g of total oU)(hm) Place TlIlI! Atk.H!lx nCI0 nClI nCI2 nCI3 nCI4 nCl5 nCI6 nCI7 prt8t8ne nCI8 phytane nCI9 nC20 nC21 nC22 nC23 nC24 nC25 nC26 nC27 nC28 nC29 nC30 nCll nCl2
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,TIe SI'III'I_ !I'll 1'1_f_ SI'Il£llId llydrocott>onQJnoentratlono IIydroc:arllcnCmcentrstlonootart (ag dry (uWlIdry~t) (ug/g dry •••~t)(!mo) wt.lll nClO nCl1 nCI2 nCl3 nCl4 nCl5 nC16 nC17 prt.otane nCl8 ~ nC19 nC20 l£21 l£22 l£23 l£24 l£25 l£26 l£27 l£28 rC29 nC30 1£31 nC32
0:00- ~ 1.0 1.5 2.3 5.6 13.5 15.6 16.0 n.a 8.2 11.3 5.4 8.1 5.7 4.0 3.0 2.2 Tt Tt Tt Tt Tt Tt 0.0 0.0 0:00.25 43.9 3.5 2.7 1.9 3.7 10.1 13.6 16.5 16.5 10.0 14.8 7.1 11.6 8.3 5.6 ).9 2.8 2.0 Tt Tt Tt Tt Tt 0.0 0.0 0.00.50 48.8 3.2 2.4 Tt 2.1 4.6 7.1 9.4 10.5 5.3 10.9 4.9 10.1 9.1 7.6 6.1 4.6 3.2 Tt Tt Tt Tt Tt Tt Tt Tt1.00 46.4 4.1 3.2 2.1 3.3 6.9 10.2 n.7 12.8 6.9 12.6 5.9 11.4 10.1 9.0 7.9 6.0 4.7 3.1 Tt Tt Tt Tt Tt 0.0 0.02.00 46.4 6.5 5.4 3.9 5.2 III n.9 19.2 16.7 12.6 17.0 9.2 13.6 n.r 12.0 12.1 11.0 10.6 9.2 8.1 6.7 5.2 5.7 'IT 5.1 Tt4.00 45.5 9.4 7.0 5.7 8.5 Bl 19.7 ~.O 26.2 21.2 27.5 15.9 27.3 27.4 22.4 20.4 20.4 19.5 17.8 16.0 12.7 11.1 10.9 Tt 9.0 Tt8.00 37.2 11.1 8.1 6.7 15.1 III 46.1 60.8 51.0 37.7 49.3 25.2 37.1 28.4 20.8 "" NA NA "" "" M NA "" M NA M
12.00 26.5 11.3 8.3 "" NA "" "" NA NA "" "" NA "" "" "" "" M "" NA "" "" NA M NA NA M18.00 27.2 10.0 8.5 7.0 n,o 35.2 50.3 67.4 71.0 52.8 69.3 JIl.9 63.7 54.6 49.2 46.9 100.3 35.1 28.1 24.7 17.2 15.3 15.8 Tt 13.1 Tt36.00 11.2 32.4 23.9 14.4 25.2 Bl 58.6 77.2 71.7 49.1 76.9 100.2 71.4 59.5 "" M "" M "" "" "" NA "" NA NA NA48.00 21.9 n.o 87.3 135.1 174.2 Bl 227.9 m.1 235.0 147.4 230.0 109.7 196.9 178.9 161.9 . 149.9 141.6 1J7.2 119.2 112.5 77.1 66.8 63.1 Tt Tt Ttn.oo 6.8 102.3 75.2 3).9 54.4 III 157,8 215.6 179.3 116.8 176.3 77.0 153.1 126.6 121.9 119.1 110.9 100.6 85.7 77.7 52.6 49.8 47.2 Tt Tt Ttw,.00 5.4 100.2 75.5 37.4 15.7 81 193.2 262.1 226.9 153.6 23f>.6 114.7 192.2 151.9 "" NA NA NA M NA NA NA NA M M M
(w,.oo) lIot.Sed. 4.07 21.72 42.63 45.95 III 48.31 51.97 100.31 22.85 43.88 22.';8 38.32 42.60 38.48 41.49 35.98 34.95 D.72 29.45 16.87 15.41 13.18 11.27 Tt Tt(ug/g)
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T1me !mface Oilftall ~IUI: Hydrocarbon Cono!nI:rat1cnIstart (ug/g of total 011)(hra) Place T1me Naph 2-MeHa I--ft!Na 2.~1.~ 1.2~ 2.3.~rlMeNa PIewtth
0:00- KB Jtn-85 233.1 1087.6 737.9 1'r 276.2 1'r tr NA0.250•.501.002.004.008.00
12.0018.0024.0048.0072.00 KB Jtn-85 190.1 1101.1 659.4 1'r 261.4 1'r 1'r NA96.00
120.00168.00 L1 Har-86 NA 542.2 BI 323.2 269.9 129.8 110.0 118.9216.00 L1 Har-86 210.2 581.1 BI 3.50.2 288.8 1:n.6 94.4 135.7********* ••*** •.•.** .•**** •.•..••.** .•***** .•.••.-- •.•**** ••• **'liM .••.•.•• $ aa••.•.•.•.••.•••••. *••**••.••••.•.•.•*•.•._* ......**2 DBy ll!athemd Pndloe Bay Crude Oil ••• J*olaf Bay Sed1m!ntll
'I':bIa !Uface OilfIOl FIJ>o<X:lUI: flydrocarbon ConoelItratiorBstart (ug/g of total oU)(hrs) Place TiDe Naph 2-MeHa I-M!Na 2.~ 1.3-d1MeNa 1.~ 2.3.~rlMeNa Ph!nanth
0:00- L1 Feb-86 213.1 384.6 235.2 387.8 295.6 145.5 155.2 1'r0.250•.501.002.004.008•.50
12.0015.2524.0048.0073•.50 L1 Feb-86 170.8 3.50.2 219.3 :n7.9 268.6 109.6 132.0 1'r
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1'1DI! arlace Oilfran FIJ>o<X:lUI: Hydrocarbon ConoelItratiorBstart (ug/g of total oU)(hrs) Place TiDe Naph 2-MeHa I-M!Na 2.~ 1.3-d1MeNa 1,2-d1MeNa2.3.~rlHeNa Phenanth
0:00- KB Feb-86 132.0 366.9 284.9 'BI 266.2 89.1 1:n.0 70.60.250•.501.002.004.008.00
12.0018.0036.0048.00n.oo96.00 KB Feb-86 18.3 217.3 199.5 BI 211.6 68.2 95.7 39.2
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DI!i'I!2l5m on. PRAS8--On:entratiOllll per liter of sea water
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T1me D1speraed 011 l't1asefl'Oll FJDoQ:am: Hydroc:arllon<llnoerd:rat1cnIstart (ug/l of sea water)(hrs) Place 1lme Naph 2-MeNa 1~ 2,H1MeMa 1,l-dJMeNa 1,:MHMeNa2,3,6-trlMeNa l'tBlanth
-0:00 KB .bt-85 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.25 KB ~ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0O.SO 1(8 .In-85 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.01.00 1(8 .In-85 0.0 0.0 0.0 0.0 Tr 0.0 Tr 0.02.00 KB .hn-85 0.0 1.1 0.8 Tr 0.8 0.0 0.6 1.24.00 KB ~ 1.4 6.1 4.5 1.1 2.2 0.8 1.1 0.88.00 1(8 .hn-85 'NA 14.4 8.2 Tr 4.1 Tr 2.0 0.0
12.00 1(8 .In-85 4.1 28.6 17.9 Tr· 7.4 Tr Tr 3.918.00 LJ ~ Tr NA HI 24.5 18.9 7.9 10.8 8.524.00 KB ~ 21.8 74.0 49.1 3.8 11.0 5.9 5.7 8.948.00 KB Feb-86 62.0 142.7 115.4 BI 101.8 38.0 49.5 Tr72.00 KB .hn-85 76.1 282.6 181.2 Tr 58.0 15.9 Tr 32.196.00 LJ Har86 57.5 122.8 BI 125.3 104.9 51.1 56.9 :rl.0
120.00 LJ Har86 75.5 149.0 HI 147.0 129.5 64.0 71.6 36.3168.00 KB Feb-86 n.5 573.9 4n.2 HI 418.3 138.7 196.2 66.0216.00 LJ Har-e6 81.3 186.7 HI 137.0 113.7 SO.6 41.4 41.7••••••••••*************** •••••••******** •••• ******* •.•***A***** •••• ******* •• ******************* ••••••*******',.2 DI1y Weath!red PNchle Bay CNde Oil lDI J*WJf Bay Sed1III!l1tB
T1JII! D1sperlIed011 Phasefl'Oll FJDoQ:am: HydrocarlxxtQlnoerltnIt1olBstart (ug/l of sea water)(hra) Place T1lIe Naph 2-MeNa 1~ 2,H1MeMa 1,301:IDteNa1.2-d»teiNa2,3,6-trlMeNa l'tBlanth
-0:00 KB Feb-86 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.25 NA NA NA NA NA NA NA NAO.SO KB Feb-86 Tr 1.4 0.7 BI 1.3 0.4 1.1 Tr1.00 KB Feb-86 0.4 1.7 1.1 BI 1.6 0.6 1.1 Tr2.00 KB Feb-86 ,Tr 1.7 2.5 BI 3.6 1.2 2.8 0.64.00 KB Feb-86 13.2 79.6 67.8 HI 67.9 25.4 36.8 14.38.SO KB Feb-86 81.5 322.5 276.8 BI zn.e 78.5 118.4 44.0
12.00 KB Feb-86 81.3 384.5 326.6 BI 276.4 104.3 136.9 66.715.25 KB Feb-86 145.4 584.5 479.8 BI 440.6 154.9 218.6 122.324.00 KB Feb-86 121.4 351.2 286.9 HI 254.2 79.4 122.9 42.648.00 KB Feb-86 87.8 272.3 223.1 BI 192.6 67.7 94.6 45.913.SO KB Feb-86 65.6 171.3 140.1 BI 126.2 43.8 62.2 22.4
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T1me Dispersed 011 Phasefrcu FJDoQ:am: Hydrocarbon<llnoerd:rat1Oll11start (ug/l of sea water)ChI's) Place '1'1t!e Naph 2-MeNa 1'*lfa 2,6-d1HeNa1,3-d1HeNa 1,2-lIDIeHa2,3,6-trlMeNa PIlera1th
0:00- lCB Feb-86 0.0 0.0 0.0 0.0 Tr 0.0 Tr 0.00.25 KB Feb-86 7.7 za.s . 18.6 HI 17.7 6.4 8.8 4.6O.SO 1(8 Feb-86 35.2 1~.6 82.0 HI 75.0 25.8 37.9 16.31.00 1(8 Feb-86 20.2 fB.7 51.6 BI SO.2 17.0 25.6 14.72.00 LJ Har-e6 62.7 366.1 BI 245.7 202.1 90.8 73.5 100.84.00 LJ Har-e6 67.2 415.9 BI 287.0 222.1 109.3 87.8 109.08.00 LJ Har-86 119.0 663.4 BI 475.0 367.4 185.9 153.9 173.4
12.00 LJ ~ 66.9 759.1 HI 5SO.4 'l/.7 .2 198.0 160.5 m.518.00 LJ ~ NA NA NA HI 839.4 207~3 415.9 Tr36.00 LJ Har-e6 Tr 499.9 BI 386.1 340.0 245.1 107.2 187.248.00 LJ Har-e6 Tr 673.9 BI 510.0 419.6 369.4 154.2 197.672.00 LJ Har-e6 0.0 425.8 HI 341.6 m.2 233.3 98.0 159.396.00 LJ ~ Tr 461.1 HI 510.2 387.5 no' 210.0 m.2
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n.. SPMPI-.m. Sl'MlAllIII FID-<I: am: ~oontxn Qxd!llUatJ.anlaUrt (uw dry (ug/l of _ .mer)(bra) wt.1l) Place '1'JJIe NIIph 2-MeNa HteHa 2.6-dDIIRa 1.3-cUH!Ra 1.2-dIM!Ma2.3.krlMeNa 1'tBwIth
-0:00- 52.9 LJ 0ct-85 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.000.25 SO.1 ICB JID-85 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00o.so 53.0 LJ 0ct-85 Tr 0.06 Tr II Tr 0.00 Tr Tr1.00 47.7 ICB JID-85 Nt\ Nt\ Nt\ Nt\ Nt\ Nt\ NA NA2.00 51.3 LJ oee-es 0.00 Tr Tr II Tr 0.00 Tr O.OS4.00 SO.1 LJ oee-es 0.00 Tr Tr II Tr 0.00 Tr Tr8.00 53.8 LJ 0ct-85 Tr 0.21 0.3> II 0.24 0.06 0.18 0.c.J
12.00 48.2 LJ oc:t-85 Tr 0.38 OM II 0.46 0.14 0.39 0.1318.00 44.4 laS .lD-85 0.00 0.65 Tr II 0.42 Tr 0.37 Tr24.00 50.4 laS .lD-85 Tr 3.02 1.93 II 1.21 Tr Tr o.n48.00 43.8 0 JID-85 1.23 7.'XJ 4.n II 2.47 0.52 1.25 1.3772.00 35.9 ICB JID-85 2.74 15.48 10.58 II 4.25 Tr 2.85 2.7596.00 'lB.7 LJ ~ 1.07 5.68 II 4.23 4.38 1.96 1.11I 2.08
13>.00 25.0 LJ ~ 1.57 7.04 II 5.36 5.23 2.23 2.01 2.11168.00 29.5 LJ MIr-86 1.17 6.54 II 5.21 5.c.J . 3.86 1.'XJ 2.29216.00 23.0 LJ ~ Tr 5.8) II 5.32 5.49 2.19 2.16 2.27
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m. Sl'MlAllIII FID-<I: am: Rydwcarboc. Qx:c:iiiillllt:1c:JlwSUit (UW dry (ug/l of _ water)(bra) wt.1l) Place '1'JJIe NiIph :Ht!NI 1~ 2.~ 1.3-d1M!Ha 1.2-dDl!Ra 2.3.krlMeNa I'herBilh
-0:00- 51.6 ICB Feb-86 Tr Tr Tr II Tr o.on o.on o.em0.25 49.3 ICB Feb-86 Tr Tr Tr II Tr o.on o.eoo TrO.SO 46.4 laS Feb-86 Tr Tr Tr II Tr o.on o.on Tr1.00 46.8 ICB Feb-86 Tr Tr
ITr II Tr o.oco Tr Tr
2.00 43.0 laS Feb-86 Tr Tr O.OSI II Tr o.on Tr Tr4.00 34.1 ICB Feb-86 o.on Tr Tr II Tr o.on Tr o.o»8.SO 41.0 laS Feb-86 O.aD Tr 0.2'XJ II 0.484 Tr Tr Tr
12.00 20.2 ICB Feb-86 o.eeo Tr 0.278 II 0.426 Tr re Tr15.25 26.4 ICB Feb-86 o.on Tr 0.438 II 0.619 Tr 0.372 Tr24.00 25.0 ICB Feb-86 o.on 1.553 1.726 II 2.448 0.823 1.799 Tr48.00 3.6 ICB Feb-86 0.193 0.410 0.206 II 0.191 Tr 0.109 Tr73.SO 3.8 laS Feb-86 0.255 0.385 0.229 II 0.181 Tr 0.088 Tr
(73.50) Bot.Sed. ICB Feb-86
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T1IIe SPM"-ftal Sl'MlAllIII FID-<I: am: Rydrocatboll Qx:c:iiiill'8tiorllstart (UW dry (ug/l of _ wter)(bra) wt.ll) Pl,ace '1'JJIe NiIph :Ht!NI 1'*Na 2.6-dDteNa 1.3-d1M!Ha 1.~ 2.3.krlMeNa l'tewlth
0:00- 48.0 KB Feb-86 o.on Tr Tr II Tr o.on Tr o.oeo0,25 43.9 ICB Feb-86 ozoo .Tr 1.'l' II Tr o.eeo Tr TrO.SO 48.8 KB Feb-86 o.on Tr Tr II Tr c.coo Tr Tr1.00 46.4 ICB Feb-86 o.on 0.070 Tr II Tr O.aD Tr Tr2.00 46.4 ICB Feb-86 Tr 0.200 0.115 II 0.134 Tr 0.076 0.1124.00 45.5 laS Feb-86 Tr 0.247 0.191 II 0;241 O.O'XJ 0.152 0.2358.00 37.2 laS Feb-86 o.en 0.195 0.190 II 0.299 Tr 0.176 O.D>
12.00 26.5 KIl Feb-86 0.000 NA -Nt\ II NA NA NA. NA18.00 27.2 laS Feb-86 o.on Tr Tr II- Tr - o.on Tr Tr36.00 1l.2 laS Feb-86 Tr Tr 0.Q61 II 0.129 Tr 0.074 0.078 .48.00 21.9 laS Feb-86 Tr Tr 0.375 II 0.831 Tr 0.561 Tr72.00 6.8 KB Feb-86 Tr Tr Tr II 0.119 Tr -Tr Tr96.00 5.4 IQl Feb-86 Tr 0.221 0.131 II o.zs .- Tr 0.122 Tr
.(96.00) Bot.Sed. laS Feb-86
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TillIe !i"H Phaseftall !i"H Losd HydrocarbonConcentrat1ons -start (118 dry (ug/g dry weight)(hrs) wt./l) Naph HteNa l-MeNa 2,&-dfHeNa1,3-d1HeNa 1,2-d1HeNa2,3,krlHeNa l't1enanth
0":00 52.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.25 50.1 0.0 0.0 0.0 0.0 0.0 0.0 . Q.O 0.00.50 53.0 Tr 1.1 Tr BI Tr 0.0 Tr Tr1.00 47.7 NA NA NA NA NA NA NA NA2.00 51.3 0.0 Tr Tr BI Tr 0.0 Tr 0.94.00 50.1 0.0 Tr Tr BI Tr 0.0 Tr Tr8.00 53.8 Tr 4.0 3.6 BI 4.4 . 1.1 3.3 1.4
12.00 48.2 Tr 7.9 8.2 BI 9.6 2.9 8.2 2.618.00 44.4 0.0 14.5 Tr BI 9.5 Tr 8.4 Tr24.00 50.4 Tr 60.0 38.2 BI 24.1 Tr Tr 15.348.00 43.8 28.2 180.3 10M BI 56.3 11.8 '28.5 31.372.00 35.9 76.3 431.1 294.8 BI 118.3 Tr 79.4 76.596.00 28.7 37.3 197.8 BI 147.4 152.7 68.4 62.5 n.5
120.00 25.0 62.7 281.8 BI 214.5 m.4 89.4 80.3 84.5168.00 29.5 39.5 221.6 BI 176.8 172.1 131.0 64.2 n.7216.00 23.0 Tr 252.2 BI 231.1 238.5 95.2 93.9 98.6••.•*****,•.••..•.••.******.*** ••••******** •• **••*******.**************************a**a.*.A****A***aA*A************
1'JIIe !i"H Phasefrllll !i"H Losd ItjdroaIrbOli CmceiItratiomstart (118 dry (ug/g dry weight)(hrs) wt./I) Naph HteNa l-MeNa 2,6-d1HeNa1,3-d1HeNa 1,2-d1HeNa2,3,krlHeNa Pherw1th
0":00 51.6 Tr Tr Tr BI Tr 0.0 0.0 0.00.25 49.3 Tr Tr Tr BI Tr 0.0 0.0 Tr0.50 46.4 Tr Tr Tr BI Tr 0.0 0.0 Tr1.00 46.8 Tr Tr Tr BI Tr 0.0 Tr Tr2.00 43.0 Tr· Tr 1.2 51 Tr 0.0 Tr Tr4.00 34.1 0.0 Tr Tr BI Tr 0.0 Tr 0.08.50 41.0 0.0 Tr 7.1 BI 11.8 Tr Tr Tr
12.00 20.2 0.0 Tr 13.7 BI 21.1 Tr Tr Tr15.25 26.4 0.0 Tr 16.6 BI 23.4 Tr 14.1 Tr24.00 25.0 0.0 62.1 69.0 BI 97.9 32.9 72.0 Tr48.00 3.6 53.6 113.8 57.3 BI 53.1 Tr :1>.2 Tr73.50 3.8 67.1 101.3 60.4 BI 47.7 Tr 23.1 Tr
(73.50) Bot.Sed. 223.4 674.6 587.6 BI 545.2 162.0 232.5 51.8
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Time !i"H Phasefttlll Sl'MLosd HydrocarbonConcentrationsstart (118 dry (ug/g dry weight)(hrs) wt./l) Naph HteNa 1~ 2,&-dfHeNa1,l-d1HeNa 1,2-d1HeNa2,3,kr1MeNa Ph!nanth
0:00- 48.0 0.0 Tr Tr BI Tr 0.0 Tr 0.00.25 43.9 0.0 Tr Tr BI Tr 0.0 Tr Tr0.50 48.8 0.0 Tr Tr Bl Tr 0.0 Tr Tr1.00 46.4 0.0 1.5 Tr- BI Tr 0.0 Tr Tr2.00 46.4 Tr 4.3 2.5 BI 2.9 Tr 1.6 2.44.00 45.5 Tr 5.4 4.2 BI 5.3 2.0 3.3 5.28.00 37.2 0.0 5.2 5.1 BI 8.0 Tr 4.7 8.1
12.00 26.5 0.0 NA NA HI NA NA NA NA18.00 27.2 0.0 Tr Tr HI Tr 0.0 Tr Tr36.00 11.2 Tr Tr 5.5 HI 11.5 -, Tr -, 6.6 7.048.00 21.9 Tr Tr 17.1 HI 37.9 Tr 25.6 Trn.oo 6.8 Tr Tr Tr HI 17.5 Tr Tr Tr96.00 5.4 Tr 40.9 24.2 HI 38.0 Tr 22.6 Tr
(96.00) Bot.Sed. Tr Tr 2.39 HI 4.41 1.01 3.14 Tr
A*A*"AMA.W"Ii.'" *i**'•• **.,'''''** ••••• - •••••••••••• **•• *,••****** ••••••• **••• ***** .•
Id!<ltlflable at'Oll'llUcs (Note: III oboeN!<! al1phaUcs)
Dl~ ~rat1ons per liter of see water
A:U••..•UUUU .•••..••.•.•..•.•.•.•.•UUUAU .•..••.••..••.U .•.•uuu".•.••uu.•.•u.•.••.••...•UU •.•.•:lAUUAU.••.AU".•.•••.••..••.••.•.••.•.•UAUU .•.•.••u•.•.••uuu •.U ••.••..•UAU:U•.•.•••.••.••••.• u•.•uU •.••.•.•.UAUUUU .•.•••.•.•.
Tbe DIssohed 1'1_ DIssol....r 1'1_f •.••• FID-a: Ibn: IIydrocarbon Olnoontratlons IIydrocarl>on Olnoontrat1onl_tart (ug/l of ••.• _er) (ug/lof _ •••••• )On) Place TIne Toluene EthylbenE p-Xyle1e o-Xyle1e a-ne "'""'-1 ••••• It!sltyle1e Naph ~ I- 2.6-d..fME!Ha I. 3-dfM:!Na I,~ 2,3,6-1:"- FIuotme ~h
0:00- KB .- 0.0 0.0 0.0 0.0 0.00 0.00 0.00 0.0 0.0 0.0 0.00 0.00 0.00 0.00 0.00 0.000.25 W Apr-86 9.0 0.7 3.2 1.7 Tr Tr Tr 1.4 1.0 0.9 0.:11 0.33 Tr, 0.00 Tr Tr0.50 KB .- 20.4 4.6 17.6 10.0 Tr Tr 0.61 3.0 2.0 1.7 0.00 Tr : 0.00 0.00 0.00 0.00
- 1.00 W Apr-86 74.1 5.5 13.9 11.2 0.48 0.61 0.87 1.7 3.6 3.3 1.20 1.18 0.37 Tr 0.47 0.492.00 KB .- moO 14.9 49.3 28.2 1.D9 1.35 1.42 12.8 8.7 7.4 1.51 0.69 Tr 0.00 0.82 0.004.00 KB .- 3lIl.3 II 88.5 48.5 1.50 2.36 2.38 24.1 15.7 13.4 2.65 1.15 1.63 Tr 1.02 0.008.00 KB .In-85 749.5 54.8 176.5 100.3 4.41 5.38 6.03 38.7 25.1 22.4 3.78 1.74 2.45 0.85 2.69 Tr
12.00 KB .In-85 629.1 43,9 133.0 83.3 ' 3.65 4.11 4.79 22.8 17.6 16.2 2.57 1.22 1.53 Tr 1.56 Tr18.00 D .In-85 595.6 43.1 135.3 810.8 3.35 3.810 4.50 27.5 19.7 18.3 2.53 1.01 1.79 1'r 1.68 1'r24.00 D .- II 15.6 57.6 38.1 1.40 1.60 2.07 23.0 15.1 14.0 2.24 1.05 1'r 0.00 1.97 Tr48.00 D .In-85 II 26.2 82.1 61.0 2.36 2.73 3.26 34.8 19.1 19.0 3.:11 1.47 1.62 0.70 2.68 1'r72.00 D .In-85 II 35.9 120.8 92.5 3.98 4.78 6.03 59.9 31.2 29.1 5.44 2.37 1.09 1.23 3.90 0.6296.00 D Feb-lI6 95.7 19.9 60.9 56.6 2.61 3.16 5.07 JIJ.3 15.0 17.8 1.52 4.98 1.1Il 1.19 2.8'J 1.13
120.00 D I'l!I>-& 55.4 13.8 50.9 45.4 2.05 2.09 4.24 40.3 13.5 17.4 1.09 4.48 1.59 1.25 3.25 1.05168.00 D I'l!I>-& 18.0 9.5 36.8 31.8 1.53 1.82 3.76 42.8 16.2 18.0 '1.45 4.33 1.58 1.31 5.27 1.22216.00 KB I'l!I>-& 4.7 4.7 20.5 24.4 1.13 1.45 3.71 29.7 13.9 16.1 1.48 4.91 1.79 1.71 7.63 0.85•••••••••••••u ••••uu ••••uu •••• .u••UUUU •.•.UAu••••••UU ••••••*•.••.••.""'.UU •.•.•.•••..•.••..•.•.••.•••.•.•.•.•.•.•uu •••••••••••••••••uU •••••••••••••••••••••uuuu •••••••u •••••••••••••••u:uu.u •.••UU ••UMU•••••••AM••••••••MUUtU
2 Iloy-...re.t Pnd10e IIoy Crude on 8I1d .-lof liliy 5ed1lEIItB
n- DIssol....r "- NaolW!d l'twJef •.••• FID-a: Ibn: IIydrocarhon Olnoontrotlons IIydrocarlJon Olnoontrotlonsstart (Ullll of ••.• _er) (ug/l of __ er)
On) Place n- Toluene Ethyl ••••• p-Xyle1e o-Xytene a-ne ","",-lberct l1es1tytene HoP> ~ .-- 2,6-<ItltoNa1,~ 1,2-dl!toIlo 2.3,6-1:"- FIuotme_h
0.00"" "" "" "" "" "" "" "" "" "" "" "" "" "" "" ""0.25"" "" "" "" "" "" "" "" "" "" "" "" "" "" "" ""0.50 KB Feb-lI6 1.6 1.4 5.3 3.6 Tr 0.45 0.70 5.3 3.5 2.7 0.69 1.04 0.42 1'r 1.48 1'r
1.00 KB I'l!I>-& 4.7 4.8 11.5 12.4 0.87 1.51 2.23 16.7 10.0 8.0 2.20 2.69 1.04 0.48 3.08 0.672.00
"" "" "" "" "" "" "" "" "" "" "" "" "" "" ""ItA
4.00 D Feb-lI6 Tr 0.0 1'r 12.5 l.oa 0.00 1.53 0.0 0.8 6.1 2.04 3.JIJ 1.11 0.72 1'r 1'r8.50 D I'l!I>-& 5.4 2.7 1'r 20.8 2.37 1.24 4.96 0.0 1.7 16.1 4.67 6.55 2.08 o.n 1'r 1'r
12.00 D I'l!I>-& 11.6 9.7 1.4 34.6 3.73 3.8'J 7.45 0.9 4.8 22.1 5.63 7.48 2.40 0.88 0.84 1'r15.25 KB Feb-lI6 7.0 5.6 Tr 20.8 1.81 2.06 3.82 0.9 3.4 16.5 3.1Il 5.47 1.69 0.1Il 28.07 Tr24.00 D I'l!I>-& 9.2 11.6 1.4 38.9 2.72 3.72 6.01 1.5 11.4 25.8 6.22 r.n 2.61 1.00 1.82 0.9248.00 KB I'l!I>-& 5.8 8.7 14.3 :11.9 2.09 3.22 5.73 23.5 24.2 21.9 4.23 5.82 1.81 0.85 1.41 1'r73.50 D Pel>«> 5.3 6.3 22.8 24.7 1.62 2.41 4.50 27.1 18.8 17.0 3.78 4.:11 1.35 1'r 1'r 0.00
••••••u ••*"** •.•.•. u ••u..... ••.••••••••••••U ••.U*"aM•••••••**•.**** •.•••.UM.u ••iIlft••altu •.••.•.•.•.•.••.•••Ut •••.•.•••••.•.•.• UlAUUAAUA •••.••. U •.••.•.•.•••U •••••••A.AAlUU •.Ull:••• U•••••••U•••M•••U uat:u •••• I
12 Iloy-...re.t l'nd1oe IIoy Crude on 8I1d -Wrolof liliy __
'nil! Of.saohted PhtaJe m-lvedl'l_f •.••• FID-a: Ibn: , Rydrorarbon Qn:entratlons llydtocttboo Contentrotions_tart ( •• 11 of ••.• woter) (ug/l of _ woter)On>' Plare 'nil! Toluene Ethylben< p-Xytene o-Xyfene a...., ","",-lberct It!sltyle1e Noph ~ I- 2,~1.~ I,~ 2,3,6-1:"- Plm •.•••• _h
0:00- D Feb-86 Tr 1'r 1'r Tr OJm 0.000 Tr 1.51 2.3 1.7 0.74 1.D6 0.44 1'r 0.59 1'r0.25 D I'l!I>-& Tr 1'r 1'r Tr OJm 0.000 Tr 4.32 4.1 3.2 0.97 1.42 0.49 1'r 0.8'J Tr0.50 D Feb-86 1'r 1'r 1'r Tr 0.000 Tr 1'r 9.75 8.0 6.3 1.41 2.32 0.85 0.42 1'r 0.441.00 KB I'l!I>-& Tr 1'r 1'r 1'r 0.000 Tr 0.57 16.06 12.5 10.1 2.51 3.28 1.19 0.55 1'r 0.682.00 KB I'l!I>-& Tr Tr Tr 0.699 Tr 1'r 1.17 7.86 24.1 21.2 4.96 6.64 2.54 0.83 1.94 1.254.00 D I'l!I>-& Tr Tr 0.000 0.513 Tr Tr 1.:11 0.51 21.2 23.9 5.82 7.67 2.99 0.96 2.17 1.468.00 D Feb-lI6 1'r 1'r 0.000 1'r 0.000 Tr 1.57 Tr 24.4 31.1 7.76 10.46 3.98 1.31 2.41 1.62
12.00 D I'l!I>-& 1'r 1'r OJm Tr 0.000 0.000 1'r Tr 1.4 2.2 1'r 1.16 0.63 0.29 0.41 1'r18.00 KB I'l!I>-& Tt Tr 0.000 1'r 0.000 0.000 0.00 Tr 1.4 0.9 Tr 0.46 0.49 1'r Tr Tr36.00 D Feb-86 1'r Tr 0.000 0.297 0.000 1'r 0.:11 Tr 3.7 8.0 4.71 6.78 2.15 0.98 0.55 0.7148.00 KB I'l!I>-& Tr 1'r Tr 0.373 OJm 0.000 1'r Tr 3.7 8.1 3.25 5.65 1.60 0.55 0.00 0.4072.00 D I'l!I>-& 1'r Tr OJm 0.556 OJm 0.000 0.00 Tr 4.0 7.4 0.77 3.:11 1.31 0.45 1.81 0.3696.00 KB I'l!I>-& 1'r 1'r 1'r 0.620 0.000 0.000 0.:11 Tr 18.8 21.0 4.32 6.64 2.52 0.92 4.29 1.31
••.•.•...•••.••..••••..•••••.•.•.•.•.•.•••••..•.••••••••.•.•.••.•.•..•.•.•.••••••.•.•.•••••••••••••.•.•.••.•.•.•.•••.•.•••.••"••.•••u•••."u•••.•.•.•••.••..,.•.••"•.,.u••.•.•.•.•••.".•.•.••.••.•.•.••.•••••.••.•.•.•.•.•.".•.•.•.•.•.•••.•.•.•...•.•.•.•."•.••.u•.•.•.•.••••.••.••.
~ <XJU2fDlA1'UIfl FlU( STIRll!D 0WIII!Il. IOO'I!RDt!Nl'S
RATIaI: ~U:19 for selected n-elkln!s 8l1d8rOl8tics
*,••.•••••.•• "A"__"""'*-""""""""_"",,,,,,,_,,_,,,,,,,, ,'**********************
T1IIefItastart(hIs)
-----------------9.aface 011.----------------------RATIa): CIllqIani/U:19
rCJ.2/ rC1.5/ Naph/ 2-M!NaIU:19 U:19 U:19 U:19
U:10/U:19
U:12/U:19
U:16IU:19
r{;19/U:19
1.00 0.96 0.66
l,3-d1HeNa/ l,2-1l1MeNaI 2,3,kr1MeNal Phenanth/U:19 U:19 nC19 nC19
0.240:00-0.250.501.00,2.004.008.00
12.0018.0024.0048.0072.0096.00
120.00168.00216.00
z.n 2.45 2.00 0.15 0.89 0.21
1.351.28
1.962.13'A'''''
1.431.54
1.001.00
*"******
0.75 0.550.68 0.44
******" 1$
0.750.28 o;n, .
0.370.38
0.180.17
***
0.150.12
**AiIIM" •• *0.160.18
*****-••••• ****** ••••• UP "
2 Dsy Weathered PtucIloe Bay Clude on 8l1dJarolof Bay Sed1JEnts
T1IIefItastart(hra)
0:000.250.501.002.004.008.50
12.0015.2524.0048.0073.50
----------------~9.afaoe O1l,-~--------------------. RATUll: 00IIIPQ.DI/U:19
rC1.2/ rC1.5/ Naph/ 2-M!NaIU:19 U:19 r{;19 nC19
r{;10/nC19
r{;12/r{;19
U:16/nC19
U:19/U:19
1.82 1.43 1.00 0.71 0.44
l,3-d1HeNa/ l,2-1l1MeNaI 2,3,krlHeNal Phenanth/U:19 nC19 r{;19 r{;19
0.56 0.27 0.29
1.21 o.so 0.63 0.48 0.20 0.24
"* **"""""*,,,******, ••********* •••••.••• ****-*-**** •••• ,****** •••••••••• ••••••• A.A.**** ••. **12 !By Weath!red Pnmoe Bay Clude 011 and Jl*olof Ilsy Sed1aents
T1IIe 9.afaoe011fran RATUll: CIllqIani/m:19start r{;10/ m:12/ U:16/ U:19/ rCJ.2/ rC1.5/ Naph/ 2-M!NaI l,3-d1HeNa/ l,2-1l1MeNaI 2,3,krlHeNal Phenanth/(hrs) nC19 nC19 ~19 nC19 nC19 nC19 nC19 nC19 r{;19 r{;19 r{;19 r{;19
0:00 Ci':32 -r:43 --r:42 --rnr ---o:9i' 0.68 -.-o:u ---0:48 0.35 0.12 0.17 0.090.250.501.002.004.008.00
12.0018.0036.0048.0072.0096.00 0.13 1.52 1.72 1.00 0.94 0.75 0.04 0.43 0.41 0.13 0.19 0.08
""*,**"",***,, •.•**,** •.•, ••• **•• **,** $ - " - " Ii *••.•,**"
RAT!(J;:~!nC19 for selected n-e1kanes and 8l'OIIIItics
DI!I'!DD on. PIWiE
**, •.**** .•••• **.••.*********** ••••••••••••••*****, .•,****,.••.****** .••..•.•*,•.**•.***** ••" .•.•.••.•.**,.••.•••.•.,*,.••.•.•..••." .•.•.••,**.•**•.•..••.•..•.••,*.••.*',,"A.'''A''''''''''
Urwe8theredPndD! Bay Crude011 and Jalolaf Bay Sediments
TW: Dispersed Oil Phaseftall RATIOS:~nC19start nC10! nCl2/ nCl61 nCl9! rCJ.2/ rCJ.5! t8ph/ 2-fteNa/ 1.J-cUHeHaI 1.2-d1HeNaI 2,3.6-tr1MeNa/ !b!nanthI(bra) , nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19
0:00- --- --- --- --- ---- ------0.25 1.22 1.00 0.87 0.54 0.00 0.00 0.00 0.00 0.00 0.000.50 0.18 0.31 1.23 1.00 0.85 0.63 0.00 0.00 0.00 0.00 0.00 0.001.00 0.53 0.67 1.63 1.00 0.78 0.54 0.00 0.00 0.00 0.002.00 0.33 0.87 1.83 1.00 0.74 0.55 0.00 0.13 0.09 0.00 0.06 0.134.00 0.55 1.67 2.17 1.00 0.84 0.60 0.10 0.46 0.17 0.06 0.08 0.068.00 0.91 1.~ 2.08 1.00' 0.92 0.65 0.67 0.19 0.09 0.00
12.00 1.00 1.88 1.88 1.00 0.81 0.45' o.n 0.73 0.19 0.1018.00 1.00 0.78 0.54 0.28 9·12 0~16 0.1224.0048.00 1.13 1.69 1.76 1.00 0.84 o.n 0.24 0.56 0.40 0.15 0.1972.0096.00 1.18 1.70 1.50 1.00 0.70 0.45 0.26 0.55 0.47 0.23 0.26 0.14
120.00 1.19 1.66 1.49 1.00 o.n 0.38 0.27 0.54 0.47 0.23 0.26 0.13168.00 1.27 1.86 1.69 1.00 0.99 0.57 0.:1> 0.56 0.41 0.13 0.19 0.06216.00 i.u 1.94 1.62 1.00 0.70 0.43 0.26 0.60 0.36 0.16 0.13 0.13••********** ••**** .•**** •..-*..*** .•******* .•*********,~***••****** ************************* •••••************************* ••,*,.••.•••••..•*****2 OIly WeatheredPndD! Bay Ctude 01.1and J*o1of Bay SediIII!nta
TW: DlBpened Oil Phaseftall RATIOS:CXllqlCUId!nC19start nCI0! nCl2/ nC16I nC19! rCJ.2/ rCJ.5! t8ph/ 2-+I!Na/ I.J-cUHeHaI 1,2-d1HeNaI 2,3,6-tdMeNa/ PIewtthI(bra) nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19
0:00- --- --- --- --- --- --- ----0.250.50 0.51 1.02 1.27 1.00 0.74 0.56 0.21 0.20 0.06 0.171.00 0.57 1.20 1.68 1.00 0.81 0.57 0.05 0.25 0.23 0.08 0.162.00 0.59 1.26 1.77 1.00 O.M 0.54 0.14 0.:1> 0.10 0.23 0.054.00 0.84 1.54 1.51 1.00 0.85 0.60 0.07 0.43 0.37 0.14 0.20 0.088.50 1.38 2.13 1.68 1.00 0.90 0.67 0.15 0.61 0.43 0.15 0.22 0.08
12.00 1.10 1.70 1.54 1.00 0.85 0.74 0.11 0.52 0.38 0.14 0.19 0.0915.25 1.06 1.69 1.60 1.00 0.90 0.73 0.13 0.53 0.40 0.14 0.20 0.1124.00 1.16 1.91 1.78 1.00 0.78 0.42 0.22 0.64 0.47 0.15 0.23 0.0848.00 1.08 1.79 1.61 1.00 0.89 0.73 0.18 0.57 0.40 0.14 0.20 0.1073.50 O.~ 1.65 1.63 1.00 0.89 0.75 0.21 0.54 0.40 0.14 0.20 0.07
AA ••••*****, .•.•.•,****,.•.•.•.•.•**** •••.***************** •••**,••.•.••.••••.•.***.•******, •..•,***** .•**************, ••••,********* ••***A*A'''A"a ••a,*
TillefI'CIII
start(hrB)
0:00-0.250.501.002.004.008.00
12.0018.0036.0048.0072.0096.00
-------------~D1spersed Oil l't!'l1Il1_Ile-------------------RATI(J;:CXllqlCUId!nC19
rCJ.2/ nC25/ t8ph/ 2-fteNa/nC19 nC19 nC19 nCl9
nCI0!nC19
nCl2/nC19
nC16InC19
nCl9/nC19
1,J-cUHeHaI 1,2-d1HeNaI 2,3.6-tdMeNa/ Ftenanth/nC19 nC19 nC19 nC19
--== --0:46 ---r.24 ---ox> --0:74 0':'580.26 1.55 1.66 1.00 0.84 0.640.37 1.79 1.78 1.00 0.70 0;590.32 1.58 1.62 1.00 0.85 0.620.39 I.M 1.49 1.00 0.68 0.380.34 1.68 1.40 1.00 0.61 0.340.35 1.74 1.51 1.00 0.62 0.370.29 1.61 1.38 1.00 0.60 0.34
1.26 1.00 0.81 0.550.19 1.42 1.43 1.00 0.64 0.380.18 1.51 1.41 1.00 0.60 0.370.13 1.32 1.40 1.00 0.67 0.38
0.97 1.24 1.00 0.80 0.56
-0:00 -0:00 0.00 0.00-0.17 0.51 0.39 0.14 0.19 0.10.0.20 0.59 0.42 0.14 0.21 0.090.15 0.65 0.36 0.12 0.19 0.110.11 0.65 0.36 0.16 0.13 0.180.10 0.60 0.32 0.16 0.13 0.160.11 0.63 0.35 0.18 0.15 0.170.05 0.58 0.32 0.15 0.12 0.17
0.36 0.09 0.180.47 0.32 0.23 0.10 0.180.53 0.33 0.29 0.12 0.16
0.00 0.43 0.:1> 0.24 0.10 0.160.:1> 0.26 0.14 0.12
*AaMA'aMt ***** ••********************a****************:•• ,.•, .•,*•..••.••.•..•****, •.****** •.,***.••.
RATICl5: ~/nCI9 far selected l\1lk.mes and aI'OIIIlt1cs
**** •• ,,*****, •.,**•..•*****, ••.••..••**.•.****, .••.********* ••••**,. •..••.•.•.•.********* .••.*** .•,**.•,*.•.•.•••.•".•.••.••..•.•..•••.,,**,.•••.•.•.•••,*•.**a'••••'**** .•.•.•****_, •.•*.~hered Pnd10e Bay CnJlIeOil lDI Jakolaf Bay Sed1DI!nts
Time SfM Phasefrca RATIaS: ~/nCI9start nCI0/ nCl2/ nC16/ nC19/ nC22/ nC2S/ Naph/ 2-+t!Na/ 1,3-d1HeNaI 1,2-d1HeNe/ 2,3,6-trlMeNa/ Pbenanth/(iml) nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19
---0:00- ---- ------0.250.50 0.51 0.32 1.03 1.00 0.79 0.48 0.14 0.001.002.00 0.00 1.05 1.00 0.82 0.56 0.00 0.00 0.134.00 0.00 1.18 1.00 0.74 0.37 0.00 0.008.00 0.00 0.38 1.37 1.00 . 0.88 0.59 ·0.21 0.23 0.06 0.17 0.07
12.00 0.54 1.41 1.00 0.90 0.59' 0.19 0.23 0.07 0.19 0.0618.00 0.56 1.01 1.64 1.00 0.82 0.56 0.00 0.18 0.12 0~1024.00 0.49 1.20 1.72 1.00 0.84 0.50 0.45 0.18 0.1248.0072.0096.00 0.50 1.28 1.32 1.00 0.71 0.44 0.06 0.34 0.26 0.12 0.11 0.13
120.00 0.64 1.51 1.47 1.00 0.68 0.46 0.10 0.44 0.33 0.14 0.13 0.13168.00 0.41 1.20 1.40 1.00 0.65 0.43 0.07 0.37 0.29 0.22 0.11 0.13216.00 0.34 1.12 1.40 1.00 0.71 0.43 0.27 0.26 0.10 0.10 0.11************************************************** •••*,•••***A********************************************************,********-**A*A*** ••2 DiIy Weath!red Pndloe Bay CnJlIeOil lDI J8kolaf Bay Sed1menta
1':lII! SfM Phasefrca RATIa;: ~/nCI9·start nCI0/ nCl2/ nC16/ nC19/ nC22/ nC25/ Naph/ Hi!Na/ 1,3-d1HeNaI 1,2-d1MeNa/2,3,6-trlMeNa/ Pbenanth/(!mI) nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19
---0:00- --r:i4 --0.43 -os -r:oo --0:62 -o:sr ------ 0.00 0.00 0.000.25 0.83 0.23 0.86 1.00 0.75 0.60 0.00 0.000.50 0.69 0.99 1.00 0.00 0.001.00 0.48 0~25 0.90 1.00 0.72 0.43 0.002.00 0.61 0.24 0.96 1.00 0.79 0.71 - 0.004.00 0.31 0.22 0.85 1.00 0.84 0.74 0.00 0.00 0.008.50 0.48 0.58 0.96 1.00 0.89 0.65 0.00 0.20
12.00 0.28 0.22 1.16 1.00 0.81 0.60 0.00 0.1115.25 0.26 0.43 1.22 1.00 0.87 0.67 0.00 0.16 0.1024.00 0.13 0.66 1.43 1.00 0.85 0.54 0.00 0.15 0.23 0.08 0.1748.00 0.52 0.13 0.73 1.00 0.71 0.29 0.16 0.35 0.16 0.0973.50 0.67 0.20 0.1lI 1.00 0.87 0.71 0.25 0.37 0.17 0.08
Bot.ScI. 0.94 1.1lI 1.62 1.00 0.89 0.69 0.18 0.54 0.44 0.13 0.19 0.04(73.50)••.•••..•*** .•.***.••**** ••.•,***,•••.•**•••••.•.•••. •••••••••••• *****•• **.•••****',••,**************.,****,.*********** •••**-***a*a**alA**A*lAlA12 DIy Weathered PrulhJe Bay Crude 011 and Jl*olof Bay Sed1m!nts
T1JII! SfM PhasefI'CB RATIaS: ~/nCI9start nCI0/ nCl2/ nCl61 nC19/ nC22/ nC25/ Naph/ 2-ft!Na/ 1,3-d1HeNa/ 1,2-d1MeNa/2,3,6-trlMeNs/ Pbenanth/(hrs) nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19 nC19
---0:00- "0:12 --0:28 ---r.97 1".'00 --0:36 ---0:00 0.00 0.000.25 0.30 0.16 1.42 1.00 0.33 - -0.00 0.000.50 0.32 0.93 1.00 0.60 '0.00 0.001.00 0.36 0.19 1.21 1.00 0.69 0.27 0.00 0.13 0.002.00 0.48 0.29 1.41 1.00 0.89 0.68 0.32 0.21 0.12 0.184.00 0.35 0.21 1.10 1.00 0.75 0.65 0.20 0.19 0.07 0.12 0.198.00 0.» 0.18 1.64 1.00 0.00 0.14 0.22 0.13 0.22
12.0018.00 0.16 0.11 1.06 1.00 0.74 0.44 0.00 0.0036.00 0.45 0.20 1.08 1.00 0.16 0.09 0".1048.00 0.37 0.69 1.39 1.00 0.76 0.61 0.19 0.1372.00 0.67 0.22 1.41 1.00 0.78 0.56 0.1196.00 0~54 0.19 1.36 1.00 0.21 0.20 0.12
Bot.Sci. 0.11 1.11 1.36 1.00 1.08 o.eo 0.11 0.03 0.08(96.00)••*****'A*a.A'A*** ••**** •••******.*.** ****•• ******* •• ***********, •• ******* ••**** •••***** •••••••••••••••••• *** •• **************A.A***AAA
APPENDIX B
TABLE OF MATHEMATICALEXPRESSIONS
SYMBOL
kP
CP
Cw
T (T T )yz' ZX' XZ
c.~v ,(V ,V )x y z
k ,(k ,k )x y zR.~Ropkopco
cp
wz
uz
u
G
n.~
APPENDIX B
Table of MathematicalExpressions
DEFINITION
partition coefficient
concentration of oil on SPM
concentration of oil in water
shear stress exerted in the z-direction on a fluid surfaceof constant y by the region of lesser y
viscosity
energy dissipation rate
concentration of species i
velQcity component in the x- (or y- or z-) direction
dispersion component in the x- (or y- or z-) direction
reaction term for species i
reaction rate for oiled particles
oil-SPM interaction rate constant
concentration of oil droplets
concentration of SPM
rise velocity
particle settling velocity
fluid velocity in thex-direction
turbulent shear
number density of particlesof species i
B-1
APPENDIX B
Table of MathematicalExpressions
SYMBOL DEFINITIONa radius of a "collision" spherer.1. radius of particles of species i
stability constant or "sticking" factorv kinematic viscosityka lumped parameter for "sticking" and including the effects
of particle radiust timeP powermgh change in potential energy in a gravity fieldks rate of SPM - SPM interaction
B-2